Synthesis of 3-triisopropylsilyloxy-1-propyllithium (TIPSOPrLi) and the characterization of its activity in anionic styrene polymerizations at 40 °C in cyclohexane was reported. The TIPSOPrLi initiator was used to prepare α-hydroxypoly(styrene) in cyclohexane with narrower polydispersity. The results show that the polydispersity index for TIPSO-PS is higher than the measured polydispersity indices for the TIPSO-PS samples with M n≥6.8kg/mol. The narrower molecular weight distribution of the TIPSO-PS is due to an increase in the rate of styrene initiation an the enhanced initiation state is due to a reduction in intermolecular association. 13% of degree of functionality values (Fn) of 1.0 for all the polyesterene samples reveal that TIPS group is present on each polyesterene chains.