Polystyrene (PS) core–TiO2 shell composite particles and TiO2 hollow spheres were fabricated using the liquid phase deposition (LPD) method. Composite particles were prepared using PS particles as templates. Calcination of the composite particles resulted in TiO2 hollow spheres. Uniform TiO2 hollow spheres were obtained when the reaction time of the LPD process was between 4 and 8 h. Furthermore, we fabricated TiO2 hollow spheres whose inner surfaces were functionalized by Pt particles after platinized PS particles were used as templates. The Pt particles were immobilized on the inner surfaces of the hollow spheres.