A new external oxidant-free electrochemical dehydrogenative cross-coupling of xanthenes and ketones for the preparation of functionalized 9-alkyl-9H-xanthenes was developed. This method enables the formation of a new C(sp3)-C(sp3) bond through release of H2 as the major byproduct at room temperature, and features mild conditions, high atom economy, excellent functional-group tolerance, scalability and facile applications in pharmaceutical chemistry.