Syndiospecific silyloxy-functionalized polystyrene with high molecular weight was prepared using a (pentamethylcyclopentadienyl)titanatrane/MMAO catalyst system. The resulting polymer is soluble in polar organic solvents such as THF and shows good thermal stability. In addition, the compound Ni(acac)(2) was used as a catalyst in preparing authentic atactic polymer of 4-tert-butyldimethylsilyloxystyrene under the same conditions. The chemical transformation of syndiospecific poly(4-tert-butyldimethylsilyloxystyrene) also give a new polar polymer, namely syndiotactic poly(4-hydroxystyrene) which is unattainable by traditional synthetic methods.