Constructing semiconductor heterojunction with optimal structure and composition is highly desired to maximize the solar light utilization for photoelectrochemical (PEC) water splitting. Here, we reported the fabrication of BiVO4@ZnO heterojunction with a novel nanostructure for PEC water splitting via foaming-assisted electrospinning and subsequent atomic layer deposition (ALD) techniques. In such BiVO4@ZnO heterojunction, the isolated BiVO4 nanoparticles were packaged within the ZnO microbelt matrix. During PEC water splitting, the BiVO4 acts as the primary light absorber for wider solar spectral harvesting, and the ZnO prompts the transfer of the photo-excited high-energy electrons, which would render them with prolonged lifetime and enhanced separation of the photogenerated charge carriers. In addition, the microbelts architecture with a hollow channel can also effectively improve the interfacial charge separation and transportation. Accordingly, the PEC performances of BiVO4@ZnO hybrid microbelts were significantly enhanced with a photocurrent density up to similar to 0.46 mA cm(-2) (at 1.23 V vs reversible hydrogen electrode (RHE) under simulated sunlight illumination), which is 15.3 times to that of pure BiVO4 counterpart (similar to 0.03 mA cm(-2)). The photocurrent density of the BiVO4@Zn0 electrode can be further increased to 1.07 mA cm(-2) at 1.2 V vs. RHE by adding hole scavenger (NaSO3) in the electrolyte solution under AM 1.5 G irradiation. (C) 2018 Elsevier Ltd. All rights reserved.