Trifunctional photoinitiators (tPIs) based on benzophenone, anthracene, and pyrene chromophores linked to a triazine moiety are proposed as new initiating systems. In combination with an iodonium salt and a silane, these structures are able to initiate the radical polymerization RP of acrylates and the cationic polymerization CP of epoxides and vinylethers under Xe-Hg lamp, LED and very soft irradiation (i.e., halogen lamp). Upon addition of an amine, these new photoinitiators were also able to start the radical polymerization of acrylates. Excellent RP and CP polymerization profiles are obtained i.e. better than those recorded using the reference compounds (benzophenone, anthracence and pyrene). In CP, some of these compounds combined with thianthrenium salts can also be used The mechanisms involved in the different multicomponent initiating systems were analyzed by ESR, fluorescence, steady state photolysis, and laser flash photolysis experiments.