The commercially available 3,4,9,10‐perylenetetracarboxylic diimide (PTCDI) acted as a heterogeneous catalyst to catalyze aerobic oxidative synthesis of benzimidazoles, benzothiazoles, and quinoxalines from o‐substituted aniline derivatives and primary amines in high yields with oxygen as the terminal oxidant. The gram scale reaction and reusability (up to six cycles) of the PTCDI catalyst were also successful and would greatly benefit industrial applications.