New three-component photoinitiating systems consisting of a cyanine dye, borate salt, and a 1,3,5-triazine derivative were investigated by measuring their photoinitiation activities and through fluorescence quenching experiments. Polymerization kinetic studies based on the microcalorimetric method revealed a significant increase in polymerization rate when the concentration of n-butyltriphenylborate salt or the 1,3,5-triazine derivative were increased. The photo-induced electron transfer process between electron donor and electron acceptor was studied by means of fluorescence quenching and SrEt change of the fluorescence intensity. The experiments performed documented that an increase of the n-butyltriphenylborate salt concentration dramatically increases the rate of dye fluorescence quenching, whereas the increasing of the 1,3,5-triazine derivative concentration slows down the consumption of the dye. We conclude that the primary photochemical reaction involves an electron transfer from the n-butyltriphenylborate anion to the excited singlet state of the dye, followed by the reaction of the 1,3,5-triazine derivative with the resulting dye radical to regenerate the original dye. This reaction simultaneously produces a triazinyl radical anion derived from the 1,3,5-triazine, which undergoes the carbon-halogen bond cleavage yielding radicals active in initiation of a free radical polymerization chain. (C) 2007 Wiley Periodicals, Inc.