The first regio-and stereoselective difluoroalkylthiocyanation of alkynes with BrCF 2 R and KSCN has been disclosed under visible light-induced copper catalysis. The copper complex photosensitizer formed in situ not only promotes the generation of CF 2 -alkyl radicals but also facilitates the construction of C−SCN bonds, allowing the reaction to proceed smoothly without any additional photocatalysts or radical initiators. Moreover, the challenging internal alkynes can also be transformed to deliver CF 2 -derived tetrasubstituted olefins with potential applications in agricultural and medicinal chemistry.