n-BiVO4 is a promising semiconductor material for photoelectrochemical water oxidation. Although most thin-film syntheses yield discontinuous BiVO4BiVO4 layers, back reduction of photo-oxidized products on the conductive substrate has never been considered as a possible energy loss mechanism in the material. We report that a 15 s electrodeposition of amorphous TiO2 (a-TiO2) on W:BiVO4/F:SnO2 blocks this undesired back reduction and dramatically improves the photoelectrochemical performance of the electrode. Water oxidation photocurrent increases by up to 5.5 times, and its onset potential shifts negatively by similar to 500 mV. In addition to blocking solution-mediated recombination at the substrate, the a-TiO2 film-which is found to lack any photocatalytic activity in itself-is hypothesized to react with surface defects and deactivate them toward surface recombination. The proposed treatment is simple and effective, and it may easily be extended to a wide variety of thin-film photoelectrodes.