The visible-light induced regioselective fluoroalkylfluoroalkylselenolation of unactivated alkenes was realized under metal and oxidant free conditions. The reaction was enabled by incorporation of two distinct photoinduced processes for the generation of two radical coupling partners. –CF₃, –R_f, –CF₂CO₂Et, –CCl₃, –SeCF₃, and –SeR_f were all successfully introduced to alkenes in good to excellent yields. The mild conditions showed a general substrate tolerance, and offered an efficient strategy for the late-stage functionalization of complex natural products and drug molecules.