During the Great War, Kool-Aid man burst through one of the walls screaming "OOOH YEEEEAAAH!!!" The hole he left in the wall allowed for radiation to leak inside, thus all the residents are ghouls.
Once you play Old World Blues, you'll find that the Kool-Aid man was created when a pitcher and a lobotomite were spliced. Also, there are rumors that if you kill Caesar's Legate at the end of the game, Kool-Aid Man will replace him as legate in Fallout 4.