BiVO 4 films with (040) facet grown vertically on fluorine doped SnO 2 (FTO) glass substrates are prepared by as eed-assisted hydrothermal method. As imple electrochemical treatment process drastically enhances the photocatalytic activity of BiVO 4 ,e xhibiting ar emarkable photocurrent density of 2.5 mA cm À2 at 1.23 Vv s. reversible hydrogen electrode (RHE) under AM 1.5 Gi llumination, which is approximately 10-fold higher than that of the pristine photoanode.Loading cobalt borate (CoBi)ascocatalyst, the photocurrent density of the BiVO 4 photoanode can be further improved to 3.2 mA cm À2 ,d elivering an applied bias photonto-current efficiency (ABPE) of 1.1 %. Systematic studies reveal that crystal facet orientation also synergistically boosts both charge separation and transfer efficiencies,r esulting in remarkably enhanced photocurrent densities.T hese findings provideafacile and effective approach for the development of efficient photoelectrodes for photoelectrochemical water splitting.Converting solar energy into hydrogen by photoelectrochemical (PEC) water splitting is promising for sustainable energy supply. [1] Since its discovery in the 1970s,the search for robust and efficient photoanode materials remains one of the toughest challenges. [2] To achieve high photocurrent density, adequate light absorption and effective charge separation and transport are required. [3] In this regard, BiVO 4 is one of the most promising candidates owing to its intrinsic advantages of low onset potential, small band gap (ca. 2.4 eV), favorable band edge positions,a nd good aqueous stability. [4] For instance,compared to other narrow band gap semiconductors such as a-Fe 2 O 3 ,the carrier lifetime and hole diffusion length of BiVO 4 are four and one orders of magnitude longer than those of a-Fe 2 O 3 ,r espectively. [5] Nevertheless,B iVO 4 suffers poor carrier mobility and severe surface recombination, suggesting that most of the photogenerated holes are blocked in the bulk of BiVO 4 and consumed in the semiconductor/ electrolyte interfaces before participating in water oxidation reactions. [5a,6] As aresult, the reported photocurrent densities of pure BiVO 4 are still much lower than its theoretical value (7.5 mA cm À2 under AM 1.5 Gi llumination). [7] Ways to address these intrinsic drawbacks to design efficient BiVO 4 photoanodes remains very challenging.Over the past decades,s trategies for improving the PEC performance of BiVO 4 have been focused on elemental doping, [8] cocatalyst deposition, [4a, 9] heterojunction construction, [10] crystal facet engineering, [6] plasmonic enhancement, [11] and nanostructured control. [9b] Furthermore,p artial reduction of V 5+ to V 4+ can create oxygen vacancies as shallow donors without introducing foreign elements via hydrogenation, [12] or chemical reduction, [13] which is also effective to enhance the photocatalytic activity of BiVO 4 . However,e xcessive V 4+ is detrimental to the PEC performance of BiVO 4 ,b ecause larger radius of V 4+ acts as scattering centers and re...