The hydrogen production through solar water splitting could be eco-friendly, environmental-benign and sustainable, alternative to fossil fuels energy carriers. In this work, the novel heterojunction WO3/fullerene/Ni3B/Ni(OH)(2) composites were successfully fabricated through different methods. The Ni3B/Ni(OH)(2) as a needle like nanostructures were integrated into the interfaces between WO3 and fullerene. The structural phase and morphology of prepared nanomaterials were significantly modified by incorporating the Ni3B/Ni(OH)(2) as a co-catalyst. The results demonstrated that dopant element serves as the conductive electron bridges, rather than general cocatalyst, to accumulate electrons and inspire the H-2 generation kinetics over pure WO3 photocatalyst. The significantly improved hydrogen rate of evolution up to 1578 mu mol h(-1) g(-1) was found for hybrid photocatalyst [WO3/fullerene 1.5% Ni3B/Ni(OH)(2)] which was 9.6 times higher as compared to pure photocatalyst. The interfacial contact between co-catalyst and composite could play substantial role in effective separation and transference of charge-carriers for improved hydrogen evolution rate. Under the visible light illumination, the heterojunction nano structures inspire rapid transfer of electrons from WO3 towards Ni3B/Ni(OH)(2) to inhibit the fast recombination rate and prolong the WO3 charge-carrier's lifetime, thereby releasing more electrons with greater reducing power for hydrogen production. This work may open an avenue for the strategy and green preparation of robust photocatalysts for scalable applications in solar H-2 evolution and sustainable environment. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.