Nano-TiO2 particles were prepared by sol-gel method, of which the surfaces were coated by SiO2. The coating was achieved by the hydrolysis of sodium silicate (Na2SiO3) in ammonium chloride (NH4Cl). The surface bonding, phase constitution and chemical components of the samples were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy (XPS). The mechanism of the SiO2 coating process onto TiO2 surface was analyzed. Results show that SiO2 particles were immobilized on the TiO2 surface via Ti—O—Si bondings, which formed at the interface. The SiO2 layer on TiO2 surface was amorphous, the photocatalytic performance was decreased of the TiO2 while its stability was enhanced after surface modification.