An aminimide possessing a benzoyl substituent, 1,1-dimethyl-1-(2-hydroxypropyl)amine benzoylformimide (BFI), proved to serve as an excellent photobase catalyst. BFI decomposes smoothly by the UV irradiation to give products containing tertiary amines. The effective nature of BFI as a photo/thermal dual-base catalyst was convinced by the thermal and photoinduced polymerization of epoxide/thiol system. Based on the facts that the mixture of BFI and epoxide/thiol exhibit a long pot life in dark and that it undergoes smooth polymerization by UV irradiation and heating, it was supported that BFI serves as an efficient photo/thermal latent dual-base catalysts. It was also found that BFI initiates the free radical polymerization of vinyl monomers such as 2-hydroxylethyl methacrylate (HEMA) under the UV irradiation while the mixture of BFI and HEMA also exhibit a long pot life in dark, indicating the excellent ability of BFI as a photoradical initiator. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012