A simple and efficient electrochemical sulfonylation of organoboronic acids with sodium arylsulfinate salts has been reported for the first time. A variety of aryl, heteroaryl, and alkenylsulfones were obtained in good to excellent yields via a simple electrochemical sulfonylation of various arylboronic acids, heterocyclic boronic acids, or alkenylboronic acids with sodium arylsulfinate at room temperature in 5 h under the catalyst-free and additive-free conditions. A plausible mechanism has been proposed based on various radical-trapping and CV control experiments.