Among other photoinitiating systems, aromatic ketone based compounds have been largely exploited as photoinitiators (PIs). However, none of these compounds efficiently absorb above 420 nm. The search of novel architectures of Pis for getting an important red shift of the absorption is crucial for the use of visible lights for polymer synthesis. Novel bifunctional dyes derived from the Michler's ketone structure are proposed here as photoinitiators for the free radical polymerization of acrylates and the cationic polymerization of epoxides upon exposure to 457, 473, and 532 nm laser diodes and even to a green LED bulb at 514 nm. Excellent polymerization profiles are obtained. These original dyes exhibit a push-pull molecular character for a remarkable covering of the visible lights. The formation of the radicals and the ions in the two- and three-component photoinitiating systems is described and the initiation steps are discussed.