In this paper, the monoclinic bismuth vanadate photoanode with porous structure prepared from successive electrodeposition and metal organic decomposition (MOD) method used as photoanode for photoelectrochemical (PEC) water oxidation. The p-type CuFeO2 ultrathin layer is coupled to form a p-n heterojunction, further promoting charge transfer and inhibit carrier recombination. The NiFe layered double hydroxide (NiFe-LDH) is electrodeposited as oxygen evolution cocatalyst (OEC) for the hole extraction for the water oxidation. Therefore, the BVO/CFO/NiFe LDH heterostructure photoanode exhibits the boosted PEC performance, achieving the a photocurrent density of 4.34 mA·cm−2 at 1.23 V vs RHE and enhanced photoconversion efficiency of 2.48%, which is 3.78 and 5.28 times higher than that of pristine of BiVO4. The heterostructure photoanode exhibits excellent PEC activity, which can provide a promising and simple strategy for fabricating photoanodes with high-efficiency oxygen release promoters.