Functionalized syndiotactic polystyrene (sPS) copolymers, including sPS-graft-atactic polystyrene (aPS) copolymer or sPS-graft-poly(methyl methacrylate) (PMMA) copolymer, were synthesized and characterized. sPS has been synthesized by using half sandwich titanocene/methylaluminoxane catalyst in homogenous conditions. Then, alpha-phenyl chloroacetylation of sPS was accomplished in a heterogeneous process by using carbon disulfide as dispersing medium and alpha-phenyl chloroacetyl chloride and anhydrous aluminum chloride as acetylating agent and catalyst, respectively. The graft copolymer of sPS with aPS or PMMA were synthesized by atom transfer radical polymerization using alpha-phenyl chloroacethylated sPS as initiator and CuBr and bipyridine as catalyst. The structure of obtained copolymer was investigated by H-1 NMR, FTIR spectroscopy, and thermal behavior of copolymers was performed by differential scanning calorimetry analyses. (c) 2007 Wiley Periodicals, Inc.