The synthesis of syndiotactic polystyrene (sPS) catalyzed with Cp*Ti(OBz)(3)/MAO/TIBA and toluene as the solvent and the effects of polymerization temperature and the external addition of TIBA on polymerization behavior were investigated. The study revealed that catalytic activity increased with polymerization temperature. The greatest activity, 619 kg sPS mol(-1) Ti h(-1), was exhibited up to 90 degrees C. TIBA also improved catalytic activity. The molecular weight of the polymer obtained decreased with polymerization temperature and the amount of TIBA. The structure and properties of syndiotactic polystyrene were characterized by C-13-NMR, FTIR, DSC, and GPC methods. It was confirmed that the sPS obtained featured all-trans planar zigzag conformation and higher syndiotacticity, molecular weight, and melting point. (c) 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 501-505, 2007