A novel and efficient copper-catalyzed cascade cyclization/trifluoromethylthiolation of unactivated olefins has been achieved with the stable and readily available AgSCF3 as the SCF3 source. A range of SCF3-substituted pyrrolines have been easily obtained under mild conditions in good yields via the present process. This method represents a facile and rapid access to valuable pyrrolines with fluorine-containing groups, and it is amenable to gram-scale synthesis.