The SiO2@TiO2-Ag@SiO2 core-shell microspheres were prepared with monodispersed SiO2(Stöber mothod) as core using sol-gel method, interface deposition method and surfactant template in turn. The structure and morphology of microspheres were investigated and analyzed by FT-IR, SEM, XRD, UV-vis, N2 adsorption desorption and XPS. The results show that average pore size and specific surface area of SiO2@TiO2-Ag@SiO2 microspheres is 2 nm, 72.73 m2/g, respectively. TiO2 diffraction peaks of anatase phase are not observed in XRD under the influence of the outer layer SiO2. UV-visible diffuse reflectance spectroscopy confirms that the core-shell microsphere is absorbed at 365 nm. Under simulated solar light source, the photocatalytic decolorization rate of methylene blue was 97.6% by SiO2@TiO2-Ag@SiO2. And the decolorization rate of methyl orange was 99.7% with 40 min flocculation precipitation under natural light.