Novel hyperbranched copolymers were successfully synthesized by the controlled charge transfer complex inimer and living radical copolymerization of p-(chloromethyl)styrene (PCMS) and acrylonitrile (AN). The resulting copolymers were characterized by SEC, NMR, FTIR, DSC and elemental analysis etc.. The influences of reaction conditions, such as the polymerization temperature, the catalyst (CuBr) concentration and the monomer ratio, on the resulting copolymers were investigated in detail. The monomer reactivity ratios were evaluated to be r(PCMS)=0.937 and r(AN)=0.088 respectively by the Fineman-Ross method. The higher are the polymerization temperature and the ratio of catalyst to monomer, the higher is the branching degree of the resulting copolymer. When the amount of monomer AN was used in excess than that of the monomer PCMS in the raw feed, the hyperbranched predominantly alternating copolymers HP[PCMS-co-AN] could be obtained. These hyperbranched copolymers were successfully used as functional macroinitiators to synthesize the star-shaped poly(PCMS-co-AN)/poly(MMA) block copolymers.