TiO2-coated SiO2 (TiO2-SiO2) particles were prepared by a layer-by-layer assembly technique using TiCl4 as a precursor. Then PEG2000 was added in the particles. Effects of PEG2000 on the formation and photocatalytic activity of TiO2-SiO2 were studied. The results show that the amount of TiO2 on the surface of the particles was increased with more coating layers. With PEG addition to the precursor solution, many fine pores in the particles appeared among the TiO2 particles and the surface area of TiO2-SiO2 was increased. The mixed crystalline phases of anatase and rutile were synthesized by 550 oC calcination, and the relative content of anatase phase increased with increasing of PEG2000 amount. The catalytic activity of PEG2000-added TiO2-SiO2 was higher than that of TiO2-SiO2 without addition.