A straightforward strategy for direct access of C9-functionalized N-alkyl-acridanes in good to excellent yields has been established via a metal- and external oxidant-free sustainable electrochemical C(sp³)–C(sp³) cross-dehydrogenative coupling reaction between acridanes and benzo fused lactones at ambient temperature. A broad substrate scope with superior functional-group tolerance via anodic oxidation of acridanes permitted the synthesis of a vast spectrum of fluorescence-active acridanes with high quantum yields.