Effectiveness and stability of photocatalyst are of importance not only for improving H-2 evolution, but also for the realization of enhanced semiconductors property in practical applications. In this study, a novel MoO3@Ni2P hybrid nanostructure is successfully prepared by a two step strategy of one-pot pyrolysis followed by calcination method. The reasonable design and controllable preparation of MoO3@Ni2P make it exhibit much high photocatalytic activities for H-2 evolution with about 39.8 and 15.8 times compared to the pure MoO3 and Ni2P. This prominently increased effect is certified by results of various characterization such as SEM, TEM, XRD, XPS, BET, FT-IR, UV-vis DRS, transient photocurrent, steady-state fluorescence, transient-state fluorescence and Mott-Schottky studies etc. The investigation indicates that the assembly of Ni2P nanoparticles and MoO3 can provide more active sites and accelerate the transfer of electrons. Moreover, the possible mechanism of photocatalytic H-2 generation is proposed. (C) 2018 Elsevier Inc. All rights reserved.