Newly developed benzophenone derivatives in combination with an iodonium salt (and optionally N-vinylcarbazole) or amines have been used as photoinitiating systems. Their abilities to initiate cationic photopolymerization of epoxides and/or radical photopolymerization of acrylates under very soft visible halogen lamp, LED and laser diodes irradiations have been investigated. One of them (BPD5) is particularly efficient for the cationic and radical photopolymerization of an epcocide/acrylate blend in a one-step hybrid cure and leads to the formation of an interpenetrated polymer network IPN upon the house hold blue LED bulb exposure (1 min for getting tack free coatings). The performances attained with some derivatives are better than those obtained with camphorquinone, used as reference photoinitiator, highlighting their high initiating abilities. These systems can be useful to overcome the oxygen inhibition for very low light intensity. The photochemical mechanisms are studied by molecular orbital calculations, fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques.