The article presents a highly effective strategy for photopolymerization of acrylates via photolatent redox-accelerated reaction based on the synergistic photoinitiating systems containing photolatent superbase and readily available peroxides. Polymerization of acrylates could be instantly initiated with the effective interaction between the photogenerated amine and peroxides. Due to the persistent interaction of produced longeval amine with peroxides, remarkable post conversion after irradiation, which is significant for radiation crosslinking of photo-screened materials, was thus initially achieved in photoinitiated free radical polymerization. To explore the synergistic interactions of the photoinitiating systems, the effect of peroxide structures and QA-DBU:BPO ratios had been examined by RTIR, showing that all peroxides are applicable as the final conversion rate of acrylates is concerned. Further, BPO and CHP significantly accelerated the photopolymerization rate in air atmosphere. The synergistic efficiency of QA-DBU and BPO as a photopolymerization initiatiation system was close to that of the conventional D-1173 photoinitiator. (C) 2012 Elsevier Ltd. All rights reserved.