Bismuth vanadate photoanode has shown great potential for photoelectrochemical (PEC) catalysis, but it needs to be further modified because of its relatively low charge-separation efficiency and poor stability. Herein, the bimetallic phosphide NiCoP decorated Mo–BiVO₄ is fabricated through the electrodeposition and drop-casting method, which significantly improves the charge separation and surface oxidation reaction. Therefore, the fabricated NiCoP/Mo–BiVO₄ photoanode exhibits a low onset potential of 0.21 V (vs. RHE) and high photocurrent of 3.21 mA cm⁻² at 1.23 V (vs. RHE), which is 3.12 times higher than that of pure BiVO₄. Importantly, the decoration of NiCoP significantly improve the stability of BiVO₄ photoanode.