Two multi-nuclear titanium complexes [Ti(η^5-Cp^*)Cl(μ-O)]3 (1) and [(η^5-Cp^*TiCl)(μ-O)2(η^5-Cp^*Ti)2(μ- O)(μ-O)2]2Ti (Cp^* = C5Me5) (2) have been investigated as the precatalysts for syndiospecific polymerization of styrene. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, complexes 1 and 2 display much higher catalytic activities towards styrene polymerization, and produce the higher molecular weight polystyrenes with higher syndiotacticities and melting temperatures (Tm) than the mother complex Cp^*TiCl3 does when the polymerization temperature is above 70℃ and the Al/Ti molar ratio is in the low range especially.