C,N,S-tridoped TiO2 hollow spheres (labeled as C,N,S-THs) were synthesized using carbon spheres as template and C,N,S-tridoped TiO2 nanoparticles as building blocks. The structure and physicochemical properties of the catalysts were characterized by Xray diffraction (XRD), scanning electron microscopy (SEM), UV-Vis diffuse reflectance spectrum (DRS), N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy (XPS) and Photoluminescence emission spectroscopy (PL). The results showed that the hollow spheres had average diameter of about 200 nm and the shell thickness was about 20 nm. The tridoped TiO2 hollow spheres exhibited strong absorption in the visible-light region. C,N,S-tridoped could narrow the band gap of the THs by mixing the orbit O 2p with C 2p, N 2p and S 3p orbits and shift its optical response from ultraviolet (UV) to the visible-light region. PL analysis indicated that the electron-hole recombination rate of TiO2 hollow spheres had been effectively inhibited when doped with C, N and S elements. The photocatalytic activities of the samples were evaluated for the degradation of X-3B (Reactive Brilliant Red dye, C.I. Reactive Red 2) aqueous solution under visible-light (lambda > 420 nm) irradiation. It was found that the C,N,S-tridoped TiO2 hollow spheres indicated higher photocatalytic activity than commercial P25 and the undoped counterpart photocatalyst.