The use of a photocatalyst (tris(2-phenylpyridine)iridium [Ir(ppy)(3)]) being able to generate both radicals and cations to initiate free radical polymerization and ring opening polymerization is presented. Remarkably, under soft irradiations (fluorescence bulb, sunlight), excellent cationic polymerization profiles and final conversions are obtained. The involved mechanisms are investigated by ESR experiments.