A transition-metal-free electrochemical chalcogenative cyclization of 2-alkynyl aryl oxime with dichalcogenides has been established to assemble valuable 4-organochalcogen isoquinolines concisely. This protocol proceeds via constant electrolysis in a user-friendly undivided cell setup. It circumvents the necessity of transition metal catalysts, chemical oxidants, and harsh reaction conditions. The practical utilities of the current protocol were illustrated by excellent functional group tolerance, remarkable regio-selectivity, easy scalability, mild reaction conditions, and transformable 4-organochalcogen isoquinoline products.