The double heterojunction of Pr2Sn2O7@Bi2Sn2O7/TiO2 composite was prepared by one-step hydrothermal method using TiO2 electrospun nanofibers as substrate. The structures were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet (UV)-visible diffuse reflectance spectroscopy and photoluminescence. The performance of photocatalytic hydrogen production over the composite catalyst was studied under UV-visible light. The Pr2Sn2O7@Bi2Sn2O7/TiO2 composite nanofibers showed high photocatalytic activity for hydrogen production. The hydrogen production rate reached 587.1 mu mol h(-1) g(-1), which was 2.7 and 7.1 times that of Bi2Sn2O7/TiO2 and TiO2, respectively. The main reasons for the high photocatalytic activity included broadened spectral range, 4f-4f transition from Pr3+ of Pr2Sn2O7 and increased separation of the photogenerated carriers by double hetemjunction via direct Z-scheme transfer.