Through hydrothermally growing SrTiO3 cubics on the surface of electrospun TiO2 nanofibers, SrTiO3/TiO2 nanofibers heterostructures were successfully fabricated in the present study. This process is able to ensure uniform distribution of SrTiO3 on the surface of TiO2 nanofibers and lead to close contact between SrTiO3 and TiO2, which is beneficial for the fast separation of photogenerated electrons and holes so as to suppress the recombination of photogenerated electrons and holes at the interphase of SrTiO3 and TiO2. Besides this, the long 1D fibrous structure easy for electron transfer, the hierarchical structure promoting mass transfer and allowing more light reflection and absorption, and the large specific surface area providing more reactions sites to facilitate the reactants to desired oxidation places all together create a synergistic effect on improving the photocatalytic activity of the hierarchical SrTiO3/TiO2 nanofibers heterostructures. Under the irradiation of UV light, in a water/methanol sacrificial reagent system, the SrTiO3/TiO2 nanofibers heterostructures generate five times more H2 than bare TiO2 nanofibers because of its high photocatalytic activity.