I found a list from 2007 that lists 25 top advertisers. #1 is Procter and Gamble. http://wiep.net/talk/seo/online-ad-spending-of-the-top-25-us-advertising-companies/

Advertising Age has a report available for purchase. It's expensive. I'm not sure what you need the info for. It may be worth it depending on your use. http://adage.com/datacenter/article?article_id=127791

There's another data page in Ad Age that lists the rank for US advertising. http://adage.com/marketertrees08update/#25 The database is an excerpt from the full report.
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Oil companies spend big on advertising

ANCHORAGE - Oil companies have spent more than $1.4 million in the last months.

The Alaska Oil and Gas Association spent more than $800,000 on ads and public relations last fall,

Conoco Phillips spent about $600,000 in December 2007 alone on advertising.

General Electric announced its $90 million advertising campaign. In May 2005

Marc-Andre Gagnon and Joel Lexchin of Toronto's York University found that American drug companies spent US$57.5 billion on promotional activities in 2004.

IBM Corp and Microsoft Corp were the top two advertisers in b2b magazine ad spend in the US in 2006, according to data from TNS Media Intelligence. IBM spent an estimated $92.9 million on b2b print ads, up 12.9% from $82.3 million in 2005, while No.2 Microsoft spent an estimated $67.4 million, down 16 per cent from $80.2 million in 2005.

AT&T, however, increased its spending on b2b print ads from $5.4 million in 2005 to an estimated $23.2 million last year, up 330%.

Hewlett-Packard Co,The third largest advertiser in b2b magazines last year which spent an estimated $47.3 million, up 10.8% from 2005.
Source(s):
http://juneauempire.com/stories/021808/sta_248201939.shtml /Oil Companies

http://news.aol.com/newsbloggers/2008/01/04/drug-companies-spend-more-on-ad...

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If you want to get a handle on the current biggest online spenders, I think you're going to have to do some intelligent guesswork from the available data.

I can't even find an up-to-date report with that kind of detail available for purchase, never mind for free.

But there are two useful data sources that you can combine that will help you get a handle on what might be happening. Depending on what you want to do with the info - e.g. want to target them for selling ad space to? - this may be enough for you to act on.

First, this report from IAB/ PwC gives you a good picture of US online advertising in 2008, and how it's been changing over time.

http://www.iab.net/media/file/IAB_PwC_2008_full_year.pdf

It has lots of useful info, and most relevant to your question it breaks down the spending by industry sector. It doesn't go down to individual companies, but it does tell you things like:

Sector - % of US online ad spend

Retailers - 22% ($5bn)
Financial Services - 13%
Auto - 12%
Computing - 12%
Telco - 9%
CPG & Food - 6%
Leisure & Travel - 6%
Media - 5%

CPG = Consumer Packaged Goods.

If you're after the actual companies, the best info I've seen is in the source found by @dumblonde:

http://wiep.net/talk/seo/online-ad-spending-of-the-top-25-us-advertising-companies/

However, that report was written in 2007, based on data from 2006. So if you want to make a call on what the current picture might be, take the company level data from there and then apply the trend and sector level data from the other report to take a stab at what it might look like today.

The original source orders the data by total advertising spend in all media. Just using Excel to re-jig the data into online spend order we get this:

Company - Online ad spend 2006 ($m)

AT&T 169
Walt Disney Co, 133
Verizon Communications 124
General Motors Corp, 118
Ford Motor Co, 99
Time Warner 91
Sony Corp, 74
General Electric 61
Toyota Motor Corp 56
Procter & Gamble Co, 54
DaimlerChrysler 45
Bank of America Corp, 43
Sprint Nextel Corp 38
Johnson & Johnson 34
Honda Motor Co, 34
Nissan Motor Co, 29
Unilever 28
Sears Holdings Corp, 24
Kraft Foods 23
Nestle 21
GlaxoSmithKline 15
McDonald’s Corp, 14
PepsiCo 14
L’Oreal 8
Macy’s 5

If you want more analysis than that, it'll cost you a lot more than $10. :)
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I'm going to risk an "unhelpful vote" here in the hope that my comment will help, Jason.

1)
The list that you're looking for does not exist.

Here's why:

A) The contact lists and associated ad budgets are closely guarded trade secrets that usually only a handful of people have clear access to.

The reason for this is simple: All any ad network or company has is the contacts that they rely on.

B) Advertisers will not release their true spending numbers (or even percentages of those numbers) because to stay one step ahead in the advertising game, you need to be on the bleeding edge.

2)
The generalizations that have been made in other answers are correct. To reiterate, the big companies with the biggest ad budgets spend the most money. Soft drink manufacturers, the auto industry, conglomerates like P&G, I.T. heavy hitters like Apple and MS, etc, all make up the largest ad buyers online.

3)
Of the "top 100" online advertisers, you'll find clearly diversified ad buys. They will spend a percentage of their online ad budget in each area (category, vertical, whatever) that they have identified, track the return in those areas and continually adjust the percentages. This is important when considering your question because unless you have upwards of a million dollars for a splash marketing campaign, you're going to want to very carefully narrow down the segments that your ads will do well in. Having a good "ad man" on the job (reference to Mad Men, not a sexist remark) will save you a lot of money and time.

4)
Bonin Bough, Global Director of Digital and Social Media at PepsiCo gave an insightful keynote and participated in conversation around PepsiCo's online ad strategy. I'm sorry that I don't have a public link available to the video of this but if you ask one of the Mesh organizers, I'm sure they'd slip you the video.

http://www.meshconference.com/bonin-bough/

Also, through lets call it "corporate strategy", Pepsico and specifically Bonin does have the up-to-date information that you're looking for.

0)
So, I've risked a non-answer here, Jason because an answer does not exist. You will find dated information that was relevant years ago, but without inside knowledge of the segments that you need to market in, you will not be able to uncover the true information that you're looking for.

Just as a quick side note, I am surprised that no one has mentioned adult internet advertising. Adult websites live and die in advertising and the budgets that many "companies" in this arena have must eclipse traditional heavy hitters.

If nothing else, please note that the online advertising industry is in what I refer to as a "revolution". Ad budgets are all over the map and if nothing else, it's a good time to pick up some deals in advertising if you have the right product, service, site or goal.

I sincerely hope that this is helpful.
Source(s):
I worked for a large ad network as a technical executive for 3 years.

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This data looks good, though little old.
Has been seeing lot of online ads from Vonage, Dell, Verizon, Netflix, monster.com and Scottrade.

#1 InterActiveCorp owns Ticketmaster, Expedia, Ask.com, Citysearch, Match.com, Chemistry.com, Evite, LendingTree, Hotwire and Hotels.com, so it makes sense that it is #1 advertiser on the Internet.

For May 2005, The Top Ten Advertisers in Internet (according to Nielsen NetRatings)
# Advertiser Impressions
1 InterActiveCorp 3,120,962,000
2 Vonage Holdings Corp 2,916,792,000
3 LowerMyBills.com, Inc. 2,170,360,000
4 Dell Computer Corporation 2,111,319,000
5 Verizon Communications 2,046,221,000
6 Netflix, Inc. 1,914,033,000
7 SBC Communications 1,762,111,000
8 Monster Worldwide, Inc. 1,545,699,000
9 Apollo Group, Inc. 1,468,174,000
10 Scottrade, Inc. 1,463,286,000

Here is a top 50 list for April, 2005:
http://www.clickz.com/3507981

You can pay "Nielsen" to get the current data.

Though, the following are top 10 advertisers for 2008, this data does not include Internet or B-2-B Spending!!!

Top 10 advertisers spent a total of $15.5 billion in 2008 – 15% less than the year before. Not a single one of the top 10 advertisers spent more in 2008 vs. 2007. Procter & Gamble maintained its perch as the top advertiser this year, despite a 19% decline vs. 2007.

Detroit’s Big Three automakers held on to spots in the top 10, despite double-digit percentage slashes in their ad budgets. Cerberus Capital Management (Chrysler) and Ford Motor Co. cut advertising 31% and 29%, respectively. General Motors trimmed its advertising 15%. Foreign automakers Toyota and Honda each made the top 10, but they, too, slashed their ad spend 7% and 3%, respectively.
Source(s):
http://www.internetworldstats.com/top10.htm
http://blogs.zdnet.com/ITFacts/?p=8050
http://www.nielsen-online.com/press_fd.jsp?section=pr_netv&nav=3
http://blog.nielsen.com/nielsenwire/consumer/tops-in-2008-top-advertisers-m...

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