This Glee photo contains
fedora, felt hat, homburg, stetson, trilby, boater, leghorn, panama, panama hat, sailor, skimmer, and straw hat.
There might also be
campaign hat, sunglasses, dark glasses, shades, porkpie, and porkpie hat.
Darren Criss & Lea Michele (Blaine & Rachel) sing 'Don't You Want Me' by The Human League in Season 2, Episode 14 of 'Glee' titled 'Blame it on the Alcohol'.