The present study describes the significant improvement of the PEC performance through modifications via co-doping of Mo/W and optimizing the level of surfactant (Triton-X 100; TX-100) addition to the hydrothermally synthesized BiVO4 photoanode. The photoelectrochemical performance is improved when the precursor solution contains an optimized 5 % TX-100 surfactant level. The visible light responsiveness of the semiconductor photocatalyst has been confirmed using linear sweep voltammograms under periodic chopped illumination of UV–vis and visible irradiation for H2O → O2 oxidation. Adding an optimized level of Mo and W to the precursor solution leads to modifications of the crystallites, which facilitates the water oxidation reaction and exhibits the highest photo-current of ∼0.61 mA cm−2. Selective loading of oxygen evolution catalyst (OEC) in the surface boosts the PEC performance to 1.05 mA cm−2 and significantly increases photon current conversion efficiency.