An electrochemical (bis)trifluoromethylative cyclization of N-cyanamide alkenes and alkynes is described, in which commercially available CF₃SO₂Na and readily available starting materials engaged in a novel electrochemical and sustainable process to assemble (bis)-C,N-trifluoromethylated cyclic amidines, which were previously inaccessible using known methods, with selective multiple bond formations in an undivided cell. Furthermore, this protocol also provided a rapid access to trifluoromethylated azines and amides in a controllable manner. A preliminary mechanism investigation and density functional theory (DFT) calculations were performed which revealed the possible reaction pathway.