Bismuth vanadate (BiVO4) is regarded as a potential material in photoelectrochemical (PEC) water splitting, but the photocurrent of BiVO4 photoanode is much lower than its theoretical value for the high recombination of photo‐induced charges and slow water oxidation kinetics. Here, we constructed a FeOOH/rGO/BiVO4 photoanode, in which rGO could enhance the photogenerated electron‐hole separation efficiency by transporting holes and the FeOOH could greatly accelerate the water oxidation kinetics. This novel photoanode displayed excellent PEC performance with the photocurrent density of 3.25 mA cm−2 at 1.23 V vs. RHE, 3.28 times higher than BiVO4 photoanode (0.99 mA cm−2), and long‐term stability with the Faraday efficiency of ∼98 % for 3 hours, demonstrating its great potential for PEC water splitting. The photoanode also provided a novel insight into the role of rGO to transport holes rather than electrons in improving the carrier separation efficiency.

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