Nanosized TiO2 and TiO2/SiO2 particles were prepared by hydrolysis of tetrabutyl titanate (TBOT) and tetraethyl orthosilicate (TEOS) in the TX-100 reverse microemulsion. These particles were characterized by TG-DSC, XRD, FTIR, TEM,N-2 adsorption-desorption. Their photocatalytic activity was tested by degradation of methyl orange. The result shows that TiO2/SiO2 nanoparticles are with a monodispersed spherical phase and a uniform size distribution, and TiO2 particles are dispersed on the surface of SiO2. The band for Ti-O-Si vibration in FTIR was observed, the Ti-O-Si bond increased the stability of anatase TiO2, suppressed the phase transformation of titania from anatase to rutile. And due to the addition Of SiO2, the average size of titania decreased from 38 nm in pure TiO2 to 5 nm in TiO2/SiO2. It was found, under UV light irradiation, TiO2/SiO2 particles showed higher activity than pure TiO2, and TiO2/SiO2(1/1) particles showed the highest photocatalytic activity on the photocatalytic decomposition of methyl orange, which was influenced by crystal structure, particle size, crystallinity and Surface area Characteristics.