The successful sunlight-photolyzed reversible addition-fragmentation chain transfer (RAFT) photopolymerization can be reversibly activated and deactivated by irradiation with sunlight in the absence of photocatalyst and photoinitiator. In the present work, the thiocarbonylthio compounds (dithiobenzoate, trithiocarbonate, and xanthate) can all be employed to carry out the polymerization under sunlight irradiation acting as an initiator, chain transfer agent, and termination agent. Moreover, it was demonstrated that the recyclable-catalyst-aided, opened-to-air, and sunlight-photolyzed RAFT (ROS-RAFT) polymerizations can be successfully carried out to fabricate precise and predictable polymers in the presence of the recyclable magnetic semiconductor nanoparticles (NPs). The oxygen tolerance is likely attributed to a specific interaction between NPs and oxygen.