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Novel highly active η5-pentamethylcyclopentadienyltribenzyloxy titanium catalystactivated by modified methylaluminoxane (m-MAO) was prepared for styrene syndiospecificpolymerization. The influences of the contents of trimethylaluminum (TMA) in m-MAO andexternal addition of tri-isobutylaluminum (TIBA) on the distribution of the oxidation states oftitanium were investigated in detail. The Ti (Ⅲ) is in favour of styrene syndiospecificpolymerization in higher catalytic activity.