Four alkoxyl ligand substituted indenyl titanium dichloride complexes, IndTiCl(2)(OR) (R = Me (2), Et (3), Pr-i (4), cyclohexyl (5)) were prepared, and evaluated as catalysts for the syndiospecific polymerization of styrene when activated with methylaluminoxane (MAO). Alkoxyl ligand substituted complexes showed higher catalytic activities than IndTiCl(3) (1) except for complex 5. When R = Et, the catalyst 3 showed the highest activity. A study of the steric and electronic effects of alkoxyl ligand revealed that the more electron-donating and less steric bulky R group was more suitable for the improvement of the catalytic activity. When the polymerization was carried in solution at high molar ratio of Al/Ti = 4000, the s-PS% of obtained polymer were in the range of 99.0-99.6%. The highest melting point of 276.9 degreesC was obtained by using 2 as catalyst. The influence of polymerization temperature was also investigated. The maximum polymerization activities were found at 50 degreesC for all of the above complexes, but the percentages of s-PS were insensitive to the polymerization temperature.