TiO2-SnO2-SiO2 nanocomposite photocatalysts were prepared with Na2SiO3·9H2O, SnCl4·5H2O and TiCl4 as precursors by chemistry coating processes and supercritical fluid drying (SCFD) method. Characterizations with XRD, TEM, NMR and FTIR showed that in addition to anatase type TiO2, a new active phase(Ti,Sn)O2 was also formed in the range of the studied doping concentration, The catalytic activity was evaluated by photocatalytic degradation of phenol as model reaction. SiO2 remained amphorous at all samples. It could prevent from growth of the size of nanopaticle and transformation from anatase to rutile. Compared with pure TiO2, or TiO2-SnO2 catalyst prepared by Sol-gel method, Nano-composite photo-catalyst showed significant improvement in catalytic activity, the photo-catalytic degradation rate of phenol in 7 h reached 88.7%. Application of the composite catalysts for the photocatalytic decomposition of phenol not only gave the same activity relative to pure ultrafine TiO2, but also reduced cost. The experimental results also proved that the thermal stability of TiO2 was greatly enhanced after mixing with small amount of SiO2. The optimized doping of SiO2 was 20.3%. The photo-catalyst prepared by SCFD combination technology was characterized with smaller particle size, larger surface area and higher activity.