We present a general electrochemical synthesis of sulfones from arenes and aniline derivatives with sodium sulfinates. A wide range of C-S cross-coupling products is available by this oxidant- and transition metal-free method. Both aryl and diaryl sulfones can be readily obtained, using this scalable and inherently safe one-step protocol. Since the synthesis excludes the need for additional supporting electrolyte and occurs in an aqueous electrolyte system that is easily recovered and recycled, this strategy represents a sustainable and green alternative to existing sulfonylation reactions.