The photoinitiated polymerization reactions of thiol-allyl ether and thiol-acrylate mixtures under visible light in the presence of several visible photoinitiating systems have been investigated. Remarkable high yield of conversions as well as fast rates of polymerization are observed; a photoinitiating system based on Rose Bengal/Ferrocenium salt/hydroperoxide is particularly efficient. The role of a large variety of photoinitiating systems and the mechanisms involved in the initiation step are discussed. (C) 2004 Elsevier Ltd. All rights reserved.