An electrochemical radical strategy involving alkene substrates provides a powerful approach for alkene functionalization. Herein, we described the first electrochemical synthesis of gem-bisarylthio enamines from vinyl azides and thiophenols through the C-H/S-H cross-coupling. This electrochemical oxidative cross-coupling is characterized by good functional group tolerance, affording a series of gem-bisarylthio enamines in excellent yields, and was carried out at room temperature without additional oxidant, transition-metal catalyst, or base. Notably, the reaction could be easily performed on a gram scale with good efficiency.