A new visible light photoinitiating system (PIS) containing a linked dye-coinitiator dyad and a nondissociative electron donor was evaluated and compared with unlinked three components systems. Our results show that in the physical mixture of the three component PIS, addition of the nondissociative donor decreased the Rp to a great extent, whereas in combination with the dyads an increase in Rp is observed. The results were explained based on faster intramolecular electron transfer in linked pairs and point out the importance of linked initiator in three-component PIS for the first time. This system is the first example of three-components system with a nondissociative donor that would be useful for long life coating formulation. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4325-4330