The TiO 2 /SiO 2 @Fe 3 O 4 photocatalysts were synthesized via two steps. First, the SiO 2 @Fe 3 O 4 particles were synthesized using Fe 3 O 4 as the core and tetraethoxysilane (TEOS) as silica source. Second, the anatase TiO 2 was coated on the SiO 2 @Fe 3 O 4 particle surface using tetrabutyl titanate (TBOT) as titanium source. The synthesized samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N 2 adsorption–desorption techniques and vibration sample magnetometer (VSM). The catalytic activity of TiO 2 /SiO 2 @Fe 3 O 4 catalysts for the photocatalytic degradation of Rhodamine (RhB) was evaluated under ultraviolet (UV) irradiation. The results indicated that the mean size of the 6%SiO 2 @Fe 3 O 4 particles was about 75–80nm and thickness of the homogeneous SiO 2 layer was about 2–3nm. The diameter of 50%TiO 2 /6%SiO 2 @Fe 3 O 4 microspheres was about 100nm and thickness of the homogeneous anatase TiO 2 layer was about 8–10nm. The saturation magnetization and specific surface area of 50%TiO 2 /6%SiO 2 @Fe 3 O 4 catalysts were 48.6emu/g and 495.3m 2 /g, respectively. The 50%TiO 2 /6%SiO 2 @Fe 3 O 4 microspheres exhibited the best photocatalytic performance. The conversion of RhB achieved up to 98.1% after 60min UV irradiation, and the photocatalytic reaction apparent rate constant k a was 0.05288min −1 . After used for 8 times, it also maintained high degradation rate and catalyst recovery.