<p>A photoinduced radicals-catalyzed reversible addition-fragmentation chain transfer (PRC-RAFT) polymerization that differs from the well-known photoiniferter RAFT and photoinduced electron/energy transfer RAFT (PET-RAFT) techniques is proposed based on a breakthrough discovery of the photo-radical synergy (PRS) effect, where photon and non-initiating organotellurium radicals that produced readily from ditellurium compound interact synergistically to cleave the C–S bond in chain transfer agent (CTA) to generate initiating radicals for polymerization. Unlike the photocatalysts (PCs) in PET-RAFT relying on special absorption window, the PRS is energy-matching, therefore this PRC-RAFT is capable of utilization of light in a wide range of wavelength from the visible to full NIR-I region (500–980 nm). Additionally, the “living” features and spatiotemporal control of the polymerization system are demonstrated successfully by polymerization kinetics, multiple light “on-off” cycle experiments and synthesis of block copolymers. Well-defined polymers with narrow molar mass dispersity (minimum <i>Đ</i> = 1.04) are synthesized from a broad range of monomers including methacrylates and acrylates, thanks to the high efficiency of this PRC-RAFT polymerization. Finally, green aqueous PRC-RAFT polymerization is also developed successfully by choosing hydrophilic ditellurium compound, demonstrating great promise in high-end area such as biomedical field.</p>