Hybrid polymerization of reversible complexation mediated polymerization (RCMP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization was designed via introducing the chain-transfer agent (CTA) of RAFT polymerization into a typical RCMP system. The RCMP/RAFT hybrid polymerization system manifested pseudo-first-order kinetics, and M-n increased linearly with monomer conversion, featuring "living" characteristics. In RCMP/RAFT hybrid polymerization, the reversible deactivation mechanism and the degenerative chain-transfer mechanism were found to work individually while influencing each other, which determined the molecular weight and dispersity of resultant polymers together. The influential factors, including the variety of CTA and polymerization temperature, were investigated in detail by kinetic experiments. Afterward, RCMP/RAFT hybrid polymerization was exploited to prepare block copolymers, affording a series of block copolymers with well-defined structure. Compared with RCMP, RCMP/RAFT hybrid polymerization avoids the use of unstable macromolecular iodide initiators, which may provide an alternative approach to improving the performance of RCMP.