Display omitted •W-doped BiVO4 coupling MIL-101 (Fe) is made as photocatalyst for water oxidation.•Optimizing W amounts can increase carriers without creating recombination sites.•MIL-101 reduces recombination, create active sites and improve oxidation kinetics.•A high photocurrent density of 4.00 mA/cm2 at 1.23 VRHE under AM 1.5G was obtained.•Photocurrent retention higher than 95.5% is obtained under illumination for 6300 s. Doping heteroatoms and decorating co-catalyst are intensively applied to improve photocatalytic ability of BiVO4. In this study, it is the first time to design W-doped BiVO4 coupling MIL-101(Fe) as photocatalyst for water oxidation using electrodeposition and hydrothermal processes. Similar system with Mo as dopant has been reported, but the dopant plays important roles on electrochemical performance. It is worthy to study the efficient system with different dopant. Doping amount of W is optimized to achieve high carrier density without creating serious recombination sites. MIL-101(Fe) is decorated on W-doped BiVO4 to suppress surface recombination, create accessible active sites and improve water oxidation kinetics. Optimized W-doped BiVO4/MIL-101(Fe) electrode shows a high photocurrent density of 4.00 mA/cm2 at 1.23 V versus reversible hydrogen electrode (VRHE) under air mass 1.5-global simulated light illumination without hole scavenger in electrolyte, due to large electrochemical surface area, high carrier density and small charge-transfer resistance. The W-doped BiVO4 and BiVO4 electrodes merely show photocurrent densities of 2.96 and 1.72 mA/cm2 at 1.23 VRHE, respectively. Photocurrent retention higher than 95.5% is obtained for W-doped BiVO4/MIL-101 (Fe) electrode under continuous illumination for 6300 s, suggesting lasting photocatalytic ability of this novel W-doped BiVO4/MIL-101(Fe) electrode.