TiO2/stellerite composite photocatalysts were prepared by dispersing TiO2 onto the surface of HCl, NaOH, or NaCl treated stellerite using a sol‐gel method. The materials were characterized by scanning electron microscopy (SEM), energy dispersive X‐ray (EDX), Fourier transform infrared spectroscopy (FT‐IR), BET surface area analysis, and X‐ray diffraction (XRD). HCl and NaCl modification result in the promotion of the pore formation at the stellerite surfaces and induced the microscopic changes, while the surface morphology and structure of the stellerite were almost ruined by NaOH modification. Supported TiO2 calcinated at 200°C presented anatase structure. The photocatalytic degradation activities of TiO2 loaded HCl and NaCl modified stellerite were better than that of natural stellerite, accompanied with increasing specific surface area. On the contrary, NaOH modification induced the loss of photocatalytic ability of composite due to the generation of silicates.