Here, a simple and efficient preparation of NiCoO nanoparticle modified nanoporous bismuth vanadate (BiVO) thin film and its application in photoelectrocatalytic (PEC) oxygen evolution reaction (OER) is demonstrated. The role of NiCoO in the composite electrode (BiVO/NiCoO) is twofold: OER cocatalyst and band structure modifier. It improves surface reaction kinetics for PEC OER and enhances charge separation efficiency simultaneously, which is believed to be a determining factor for the unprecedentedly high PEC OER performance of this BiVO/NiCoO nanocomposite. The photocurrent density of 3.6 mA cm at 1.23 V versus RHE in 0.1 m potassium phosphate buffered (pH = 7) electrolyte by BiVO/NiCoO is three times that of BiVO and significantly higher than most literature values. The BiVO/NiCoO nanocomposite shows/possess a high charge separation efficiency (η) of ≈72% as compared to only 23% for pure nanoporous BiVO at 1.23 V versus RHE, which demonstrates convincing role of NiCoO in the composite electrode. Both the excellent photocurrent density and great operational stability of this BiVO/NiCoO nanocomposite makes it a promising photocatalytic material for practical applications.