An efficient M₂CO₃-catalyzed (M = K or Cs) aerobic cross dehydrogenative coupling reaction of thiols was described. This reaction provided an efficient approach to unsymmetrical disulfides which are ubiquitous structures of pharmaceuticals and pesticides. This is the first aerobic oxidative CDC of thiols to unsymmetrical disulfides. The high atom-economy, easy accessibility of catalyst, O₂ as the ideal green oxidant, mild reaction conditions, and broad substrate scope demonstrate that the present methodology provides a green, attractive, and practical approach to disulfides.