Menschutkin reaction and controlled polymerization were combined to construct three types of star polymers with a branched core. Branched PVD was synthesized by reversible addition fragmentation chain transfer (RAFT) copolymerization and used as a core reagent to synthesize multiarm and miktoarm stars with poly(epsilon-caprolactone) (PCL), polystyrene, poly(methyl methacrylate), poly(tert-butyl acrylate), and poly(N-isopropylacrylamide) segments. Effects of reaction time, feed ratio, and arm length on coupling reaction between PVD and bromide-functionalized polymer were investigated, and a variety of A(m)-type stars (m approximate to 7.0-35.1) were obtained. Meanwhile, A(m)B(n) stars (m approximate to 9.0, n approximate to 6.1-11.3) were achieved by successive Menschutkin reactions, and A(m)C(o) stars (m approximate to 8.8-9.0, o approximate to 5.0) were generated by tandem quaternization and RAFT processes. Molecular weights of various stars usually agreed well with the theoretical values, and their polydispersity indices were in the range of 1.06-1.24. The arm number, chain length, and chemical composition of star polymers could be roughly adjusted by control over reaction conditions and utilization of alternative methods, revealing the generality and versatility of these approaches. These ion-bearing stars were liable to exhibit solubility different from normal covalently bonded polymers, and the chain relaxation and melting behaviors of polymer segments were strongly dependent on the macromolecular architecture.