Recently, visible-light polymerization has received increasing attention because of the development of LED sources and the innovation of photopolymerization technology, which is derived from different strategies to design photoinitiating systems such as the construction of D-π-A-type photoinitiators or the use of up-conversion nanoparticles. However, the association of electron donor and acceptor molecules to form a charge-transfer complex (CTC) for polymerization has rarely been reported. Hence, a ketoxime ester (PFO) with a pentafluorophenone ring as an electron-defect acceptor has been designed and synthesized as a photosensitizer. Our investigation results showed that CTCs could be formed by associating PFO with amines that contain electron-rich rings and process a better absorption property in the visible-light region than PFO. Moreover, the two kinds of free radicals with high photoactivity were generated from CTCs via photochemical transformation, such as intermolecular charge transfer and α-cleavage, which can play a role in initiating the polymerization of acrylate monomers, and the efficiency of initiating polymerization is higher than that of PFO alone under LED@395–425 nm irradiation.