Using Quartz particles as the repeat-agents, commercial water glass as the raw material, butyl titanate as the source of titanium, the TiO2 Membrane/ Macroporous Silica gel composite microspheres were successfully prepared. The uniformity transparent TiO2 Membrane on the surface of Silica gel microspheres(SM) was inducted by sol-gel method and dipping extracted method. The structure and performance of the microspheres were characterized by Infrared Spectroscopy (IR) and X-ray diffraction (XRD). The results showed that the composite microspheres were irregular porous materials and their average diameter was 2.18 mm. The crystal type of the TiO2 film was anatase and its average size was 15 nm. Illuminated for 7.5h, the degradation ratio of the composite microspheres was up to 85%. The properties of photocatalysis would be increased with the increasing of the amount of the quartz.