A photoinduced strategy to access α-CF₃-substituted ketones through the reaction of simple styrenes with sodium trifluoromethanesulfinate (CF₃SO₂Na) in the absence of an external photosensitizer under LED (380–385 nm) irradiation and an air atmosphere at room temperature was developed. This reaction employs the commercially available, low cost, and easy to handle Langlois reagent (CF₃SO₂Na) as a CF₃-radical source, and the reaction has advantages of mild conditions, a simple system and good functional group tolerance. Investigations indicated that the product acts as a photosensitizer and ¹O₂ coexists with O₂˙⁻ during the reaction through the energy transfer and single electron transfer process.