In this study, we introduce an efficient, metal-free electrocatalytic desulfurative protocol for forming C-N bonds by selectively activating inert C(sp3)-S bonds of alkyl thioethers. This method offers a straightforward and environmentally friendly approach for modification of heterocyclic compounds from readily accessible thioethers. Preliminary mechanistic investigations suggest that the reaction proceeds via a carbocation intermediate. Furthermore, successful synthesis on a 10-gram scale was achieved in a continuous flow electrochemical reactor.