PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO2 hollow spheres preparation. TiO2-doped SiO2 hollow spheres were obtained by using the appropriate amount of Ti(SO4)2 solution on SiO2 hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO2-doped SiO2 hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO2-doped SiO2 hollow sphere has shown higher surface area in comparison with pure TiO2 hollow spheres. The 40 wt% TiO2-doped SiO2 hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m2g-1. The photodegradation rate of MB using the TiO2-doped SiO2 catalyst was much higher than that of pure TiO2 hollow spheres.