Visible-light induced perfluoroalkylation of the α-position of aldehydes via enamines was developed. The reaction proceeds by electron donor–acceptor complexation of the enamine and perfluoroalkyl iodide without any additional redox catalyst. A variety of perfluoroalkyl groups are tolerated to give various quaternary α-perfluoroalkyl aldehydes. An example using proline-derived chiral amine gives high enantioselectivity.