Ultrathin dual layers of TiO2 and Ni have been used to stabilize polycrystalline BiVO4 photoanodes against photocorrosion in an aqueous alkaline (pH = 13) electrolyte. Conformal, amorphous TiO2 layers were deposited on BiVO4 thin films by atomic-layer deposition, with Ni deposited onto the TiO2 by sputtering. Under simulated air mass 1.5 illumination, the dual-layer coating extended the lifetime of the BiVO4 photoanodes during photoelectrochemical water oxidation from minutes, for bare BiVO4, to hours, for the modified electrodes. X-ray photoelectron spectroscopy showed that these layers imparted chemical stability to the semiconductor/electrolyte interface. Transmission electron microscopy revealed the structure and morphology of the polycrystalline BiVO4 film as well as of the thin coating layers. This work demonstrates that protection schemes based on ultrathin corrosion-resistant overlayers can be applied beneficially to polycrystalline photoanode materials under conditions relevant to efficient solar-driven water-splitting systems.