From what I can see, headshots are determined based on the 'critical' stat that certain guns have i.e. the pistol and the shotgun. you can upgrade the stat to make killing headshots a bit more prevalent...yeah headshots in resident evil dont necessarily mean death every time.
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Head shots don't work on main bosses and semi bosses etc: a fat man holding a gattling gun some where in chapter 5. But take precaution, some head shots will in fact make things worst. The enemy will evolve into a menace which will take twice the ammunition and time to destroy them. If that is the case, just shoot them off directly on the torso/ leg , this will kill them and prevent transformation. In any case if you do shoot them in the head and they evolve, safe your shotgun shells and rifle rounds and just pull out a incinerate grenade "boom" one grenade kill.
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