Titanium silicalite-1 (TS-1) catalyst was synthesized in the presence of polystyrene (PS) particles (denoted as TS-1_PS catalyst) for use in the epoxidation of propylene with hydrogen peroxide. For the purpose of comparison, TS-1 catalyst was also synthesized by a conventional method (in the absence of polystyrene particles). In the epoxidation of propylene, the TS-1_PS catalyst showed a higher conversion of hydrogen peroxide and a higher selectivity for propylene oxide (PO) than the TS-1 catalyst. Consequently, the TS-1_PS catalyst showed a higher yield for PO than the TS-1 catalyst. Characterization results showed that the high catalytic performance of TS-1_PS was attributed to the enhanced hydrophobic property of the catalyst and the suppressed formation of anatase TiO2 in the catalyst.