A visible light photoinitiator, eosin, in combination with a tertiary amine coinitiator is found to initiate polymerization despite the presence of at least 1000-fold excess dissolved oxygen, which functions as an inhibitor of radical polymerizations. Additionally, 0.4 mu M eosin is able to overcome 100-fold excess (40 mu M) 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) inhibitor, initiating polymerization after only a 2 min inhibition period. In contrast, 40 mu M Irgacure-2959, a standard cleavage-type initiator, is unable to overcome even an equivalent amount of inhibitor (40 mu M TEMPO). Through additional comparisons of these two initiation systems, a reaction mechanism is developed which is consistent with the kinetic data and provides an explanation for eosin's relative insensitivity to oxygen, TEMPO, and other inhibitors. A cyclic mechanism is proposed in which semireduced eosin radicals react by disproportionation with radical inhibitors and radical intermediates in the inhibition process to regenerate eosin and effectively consume inhibitor. In behavior similar to that of eosin, rose bengal, fluorescein, and riboflavin are also found to initiate polymerization despite the presence of excess TEMPO, indicating that cyclic regeneration likely enhances the photoinitiation kinetics of many dye photosensitizers. Selection of such dye initiation systems constitutes a valuable strategy for alleviating inhibitory effects in radical polymerizations. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:6083-6094,2009