Crystal facet dependence is an important approach for optimizing the performance of photocatalyst In consideration that there is a close correlation between the photoelectric conversion efficiencies and crystal facet, the monoclinic bismuth vanadate (m-BiVO4) with (010) and (110) crystal facets has drawn attention. We designed the Ag nanoparticles modified the (010) facet of the BiVO4 (Ag-010BiVO4) and then the Ag-010BiVO4 heterogeneous nanostructure was modified by the Fe2O3 nanoparticles. In the Fe2O3 modified Ag-010BiVO4, the (110) facet of the BiVO4 was only modified by the Fe2O3 nano-particles to construct the n-n heterojunction structure. Simultaneously, the Z-scheme system was fabricated on the (010) facet of the BiVO4, where was modified by the Ag and Fe2O3 nano-particles. We investigated its photoelectrochemical (PEC) and photocatalytic activities by the measurement of the electrochemical performance and degradation of methyl orange (MO). The Ag species in the system is only treated as the solid state electron mediator. As was expected, the Fe2O3 modified Ag-010BiVO4 heterojunction structure exhibited the highest photocurrent density and the smallest impedance. Besides, the Fe2O3 modified Ag-010BiVO4 heterojunction structure exhibited excellent redox ability and the MO could be degraded 92% after 150 min. It is worth noting that the outstanding performance should be attributed to the synergistic effect of n-n and Z-scheme system in the different facets, which facilitated the separation of holes and electrons in the opposite direction. (C) 2016 Elsevier B.V. All rights reserved.