Free radical and cationic photopolymerization reactions have been greatly utilized in various conventional and emerging applications, such as coatings, electronic circuits, digital storage and 3D precision machining. Compared with ultraviolet light induced photopolymerization, visible light induced photopolymerization presents significant advantages in irradiation safety, curing depth and equipment cost. The advantages of photopolymerization over the conventional thermal-initiated polymerization include the following: (i) Fast and controllable reaction rates, (ii) spatial and temporal control over the formation of the material, without the need for high temperatures or harsh conditions, and (iii) synergic effects and enhancement are available by using co-initiators or catalytic compounds. The present invention provides effective two-component and three-component photoinitiation systems that can simultaneously act as so-called photocatalysts that initiate different types of photopolymerization in a sequential or parallel manner.