Herein, a greener approach to the eosin Y‐Na2 catalyzed, C(sp2)−H bond azo coupling of imidazoheteroarene with aryl diazonium salts is described, under acid free conditions. This direct photoredox process resulted in the corresponding azo products in good to excellent yields. Besides, this new approach could also be applicable to anilines, which is a poorly reactive substrate by other methods. The main features of this reaction are that it provides high yields and is gram‐scalable and applicable to biologically relevant imidazoheteroarenes and ‐anilines.

A sustainable visible‐light‐mediated, eosin Y catalyzed azo coupling of imidazoheteroarenes and ‐anilines with aryl diazonium salts was achieved successfully, under acid‐free conditions. This photoredox direct C(sp2)−H bond azo coupling protocol features high efficiency, good functional group tolerance and easy scalability. Important contribution of this transformation involves the mildness of the reaction conditions as well as the potential therapeutic application of the obtained diazo based heterocyclic compounds. More information can be found in the Communication by S. Saba, J. Rafique, A. L. Braga et al. on page 4461 ff.