Semiconductor photocatalysis has two important applications: environmental remediation and H 2 production. Bismuth vanadate has attracted great interests as an ideal candidate for use as high-performance photocatalysts for visible light-driven water splitting and photoanode in photoelectrochemical cells. Single crystal film is invaluable to deepen the fundamental understanding of materials. The object of this article was to provide a brief review on the advances in the preparation of epitaxial BiVO 4 thin film, the physical and photoelectrochemical properties. The epitaxial BiVO 4 thin film could be fabricated on (001) yttria-stabilized cubic zirconia or SrTiO 3 (001) by molecular beam epitaxy, chemical vapor deposition, and, pulsed laser deposition. Three crystal structures, namely, monoclinic scheelite, monoclinic clinobisvanite, and orthorhombic, were mentioned in the literatures. The optical band gap was reported to be 2.5~2.7 eV for a direct transition. The highest photocurrent of 4.83 mA cm −2 at 1.23 V vs. the RHE was obtained at the sample with Lu 2 O 3 as a hole blocking layer.