Herein, we report a inexperienced and sustainable electrochemical technique for α-alkylation of tertiary amines with halogenated alkanes underneath undivided electrolytic situations. A Barbier−Grignard-type response on the cathode produces an organozinc reagent that reacts with an iminium ion produced on the anode to offer the α-alkylated amine. The response proceeds underneath delicate response situations with wide-ranging functional-group and substrate compatibilities, affording the merchandise in good yields. Extra importantly, convergent pair electrolysis, an excellent however difficult electrochemical method, is successfully utilized on this response system. Detailed mechanistic examine indicated that an imine ion intermediate is concerned within the response course of.