PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene (PS)colloidal particles. The reaction parameters, such as initial tetraethyl orthosilicate (TEOS) concentration, water concentration and reaction temperature, have been investigated to control the thickness of silica shells. The shell thickness was prepositional to the square root of the initial concentration of TEOS and first increased with increasing water concentration, reached a maximum at about 2.0 mol/L and then started decreasing beyond that concentration. It was also found that the shell thickness decreased firstly with the reaction temperature added, then tended to a constant. The so-synthesized PS/SiO2 core-shell particles were directly crystallized into 3-D ordered thin film, then sintered at 570 ℃ into the ordered macroporous thin film.Compared with the conditional method, the present approach avoids repeatedly filling the precursor in the templetes and save time more.