The presence of antibiotics in surface waters is paid more and more attention, which is difficult to be removed by conventional treatment technology, and photocatalytic technology is considered to be a promising method for antibiotics pollutant removal. In the present work, a novel heterojunction photocatalyst was successfully synthesized by self-template method under hydrothermal condition. The photocatalytic activity of as-prepared samples was investigated by degradation of sulfamethoxazole in aqueous solution. The BiVO4/SrTiO3 composites showed superior photocatalytic efficiency under xenon lamp irradiation. The recycling tests proved that BiVO4/SrTiO3 composite was high stability and easily separated. The degradation efficiency of BiVO4/SrTiO3 composite was also greatly influenced by active species. It indicated that approximately 50% TOC reduction was achieved after 1 h photocatalytic reaction. The intermediates were investigated by LC-MS analyses, which revealed that the bonds of CO, CS, CC, CN, isoxazole ring and benzene ring were broken by attacking of active species.