Using TiO2 particles obtained by hydrolysis of titanium oxysulfate as the precursor, polystyrene (PS) microspheres as the template, TiO2/PS complex particles were successfully deposited on Ti substrates through layer-by-layer self-assembly technique and the surfactant-assisted process at low temperature. Then removed PS spheres by two methods, TiO2 hollow spheres were attained. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to characterize the synthesized materials. The results showed that the crystallization, structure and surface morphology of TiO2/PS on the surface have a great relationship with the pH value of treating solution. Diversity effects on surface integrity and bioactive of hollow spheres happened due to different ways of removing PS core.