This article presents simple and efficient 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-promoted Heck-type alkene perfluoroalkylation under visible light irradiation. With DBU as both a halogen bond acceptor and a base, these transformations can smoothly proceed via a radical process in the absence of an additional photocatalyst. The developed protocol employs alkenes and perfluoroalkyl iodides as readily available substrates and ethyl acetate as a green solvent, affording various perfluoroalkylated alkenes in satisfactory yields under mild conditions.