The synergistic mechanism of hydrogen treatment technology and heterogeneous structure was firstly reported to enhance the photoelectrochemical properties of SrTiO3/TiO2 composite. The SrTiO3 nanoparticles were successfully synthesized on the surface of TiO2 nanotube arrays to form SrTiO3/TiO2 heterostructure by a hydrothermal method. The heterogeneous structure was further optimized by hydrogen treatment under calcinadons to prepare the hydrogen-treated SrTiO3/TiO2 nanotube arrays heterojunction composite (H-SrTiO3/TiO2). The photoelectrochemical performance of H-SrTiO3/TiO2 was significantly enhanced, whose photocurrent density was 3 times of that of hydrogen treated TiO2 (H-TiO2) and 1.5 times of that of SrTiO3/TiO2 heterostructures. The improved photoelectrochemical performance of H-SrTiO3/TiO2 can be attributed to the synergistic effect of hydrogen treatment and heterojunction, which results in the enhancement of light absorption and the increase of photogenerated carrier concentration.