An electrochemical or photoelectrochemical regioselective polyfluoroalkylation/cyclization cascade of 3-aza-1,5-dienes with sodium fluoroalkanesulfinates is presented. This protocol proceeds with a broad substrate scope and good functional group tolerance under mild, oxidant-free, transition-metal-free, and electrolyte-free conditions to provide 3-polyfluoroalkylated 4-pyrrolin-2-ones in one step from readily available N-vinylacrylamides, and it is readily scalable to the Gram scale.