A recyclable solid-state photoinitiator based on the surface modified niobium hydroxide is prepared and successfully introduces into reversible addition-fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed by gel permeation chromatography analysis that well-defined polymers with controlled molecular weight and narrow polydispersity index can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to external stimulus and when light is removed from the system polymerization stops almost immediately. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. At last, the mechanism for the light initiated polymerization is proposed to illuminate how the initiation and chain propagation proceed. This facile, green and visible light initiation methodology could attract more and more applications in polymer science with the depletion of fossil energy. A recyclable solid-state photoinitiator based on the surface modified niobium hydroxide was prepared and successfully introduced into reversible addition-fragmentation chain transfer (RAFT) polymerization under visible light illumination. It is revealed that well-defined polymers with controlled molecular weight and narrow polydispersity index (PDI) can be achieved when the feed ratio of photoinitiator to the RAFT agent was controlled properly. It is also found that the polymerization is highly responsive to light initiation. In addition, the photoinitiator can be recycled and reused to initiate the polymerization for many times without significant decrease of initiation efficiency. (C) 2014 Wiley Periodicals, Inc.