Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1-ANH8) have been prepared and combined with an iodonium salt (and optionally N-vinylcarbazole) or an amine (and optionally 2,4,6-tris(trichloromethyl)-1,3,5-triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (approximate to 12 mW cm(-2)), laser diode at 405 nm (approximate to 1.5 mW cm(-2)) or blue LED centered at 455 nm (80 mW cm(-2)). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well-known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin-trapping techniques. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2860-2866