All weapons with the exception of Pharah, McCree's secondary, Junkrat, Mei's primary, Reinhardt, Winston, Zarya, Ana (on friend or foe), and Symmetra can headshot. Damage reflected by Genji can headshot as well as the initial arrows for each Hanzo's abilities (though the scattered projectiles and dragon themselves cannot). Roadhog's Whole Hog ultimate can headshot. Other abilities and all melee attacks cannot headshot.
Updated to add the most recent character, Ana, to the list of characters that can not get headshots.
Nathan K
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