Abstract Anodic oxidation of a series of structurally different Schiff bases ( 1a – 15a ), prepared from o-phenylendiamine, o-aminophenol, 3-amino-4-hydroxycoumarine or 3,4-diaminocoumarine and corresponding aromatic aldehyde, were performed in acetonitrile-tetraethylammonium perchlorate electrolyte solution at platinum using controlled potentials. As a result of two-electron oxidative cyclodehydrogenations several 1,3-oxazoles derivatives (1b–10b) and 1,3-imidazoles derivatives (11b–15b) were prepared in the yields ranging from 60 to 90%. A mechanism rationalizing the formation of 2-anisylbenzimidazole, 11b , and 2-anisylbenzoxazole, 3b , has been studied by lsv, cpsv, rde, coulommetry and preparative scale electrolysis.