A novel and simple Z-alkene synthesis by the photocatalyzed coupling reactions of alkylpyridium salts, which were prepared from primary amines, with terminal aryl alkynes at room temperature is reported here. A wide range of primary amines, which contain different functional groups, were tolerated under these conditions. The mild reaction conditions, broad substrate scope, functional group tolerance, and operational simplicity make this deaminative coupling reaction a valuable method in organic syntheses.