Splitting of water into hydrogen and oxygen has become a strategic research topic. In the two semi-reactions of water splitting, water oxidation is preferred to the four-electron-transfer process with a higher overpotential (η) and is the decisive step in water splitting. Therefore, efficient water oxidation catalysts must be developed. IrO x and RuO x catalysts are currently the most efficient catalysts in water oxidation. However, the limited reserve and high prices of precious metals, such as Ir and Ru, limit future large-scale industrial production of water oxidation catalysts. In this study, we tune inert Ni-foam into highly active NiOOH/FeOOH heterostructures as water oxidation catalysts via three-step strategy (surface acid-treating, electroplating, and electrooxidation). NiOOH/FeOOH heterostructures as water oxidation catalysts only require η of 257 mV to reach a current density of 10 mA cm-2, which is superior to that of IrO2/Ni-foam (280 mV). The high electrochemically active surface area (72.50 cm2) and roughness factor demonstrate abundant interfaces in NiOOH/FeOOH heterostructures, thus accelerating water oxidation activity. The small value (4.8 Ω cm2) of charge transfer resistance (R ct) indicate that fast electronic exchange occurs between NiOOH/FeOOH heterostructures catalyst and reaction of water oxidation. Hydrogen-to-oxygen volume ratios (approximately 2:1) indicate an almost overall water splitting by the double-electrode system. Faraday efficiency of H2 or O2 is close to 90% at 2:1 hydrogen-to-oxygen volume ratio. NiOOH/FeOOH heterostructures exhibit good stability. The results provide significance in fundamental research and practical applications in solar water splitting, artificial photoelectrochemical cells, and electrocatalysts.