Rational regulation of photogenerated carrier separation and transfer is a significant strategy to optimize the photocatalytic activity. Given that the synergistic effect of crystal-face engineering and interfacial heterojunction modification, selective deposition of Ag2O nanoparticles onto BiVO4 (040) facet has been realized successfully via the surfactant-assisted hydrothermal method combined with a facile coprecipitation process. As expected, compared to pure BiVO4 and Ag2O, BiVO4 (040)/Ag2O heterostructures have revealed great enhancements in photocatalytic O-2 evolution and methylene blue (MB) degradation capacities no matter under UV, Vis or NIR light irradiation. In-depth investigations confirm that the pronounced photooxidation performances are attributed to not only the outstanding capability in harvesting photon energies spanning from ultraviolet (UV) to near-infrared (NIR) regions, but also the accelerated charge carrier separation boosted by the charge density redistribution inside the BiVO4 homojunction.