Engineering the multi-hetero-junctions in semiconductor photocatalysts has been recognized as a promising way to achieve highly efficient photocatalytic solar-fuel generation, because the photoinduced heterointerfacial charge transfer can greatly hinder the recombination process of charge-carrier in photocatalysts. In this work, we fabricated copper species nanocrystals/TiO2 multi-hetero-junction photocatalysts through in situ reduction of CuO nanocrystals in CuO/TiO2 electrospun nanofibers by a hydrothermal method assisted by glucose. By changing the concentration of glucose, the composition ratio of copper species nanocrystals, including CuO, Cu2O, and Cu, can be adjusted in multi-hetero-junction nanofibers. Upon simulated sunlight irradiation, the optimal copper species nanocrystals/TiO2 multi-hetero-junction nanofibers exhibited an H-2 evolution rate of similar to 10.04 mu mol h(-1), a 17.3 times increase over that of bare TiO2 nanofibers (similar to 0.57 mu mol h(-1)).