BiVO4 films were prepared by a simple electrodeposition and annealing procedure and studied as oxygen evolving photoanodes for application in a water splitting photoelectrochemical cell. The resulting BiVO4 electrodes maintained considerable photocurrent for photo-oxidation of sulfite, but generated significantly reduced photocurrent for photo-oxidation of water to oxygen, also decaying over time, suggesting that the photoelectrochemical performance of BiVO4 for water oxidation is mainly limited by its poor catalytic ablity to oxidize water. In order to improve the water oxidation kinetics of the BiVO4 electrode, a layer of FeOOH was placed on the BiVO4 surface as an oxygen evolution catalyst using a new photodeposition route. The resulting BiVO4/FeOOH photoanode exhibitied significantly improved photocurrent and stability for photo-oxidation of water, which is one of the best among all oxide-based phoatoanode systems reported to date. In particular, the BiVO4/FeOOH photoanode showed an outstanding performance in the low bias region (i.e., E < 0.8 V vs RHE), which is critical in determining the overall operating current density when assembling a complete p-n photoelectrochemical diode cell. The photocurrent-to-O-2 conversion efficiency of the BiVO4/FeOOH photoanode is ca. 96%, confirming that the photogenerated holes in the BiVO4/FeOOH photoanode are indeed excusively used for O-2 evolution.