Most of the current electrocatalysts for the methanol oxidation reaction are precious group metals such as Pt, Pd, and Ru. However, their use is limited due to their high cost, scarcity, and issues with carbon monoxide poisoning. We developed a simple method to prepare a nickel foam (NF)-based monolith electrode with a NiO nanosheet array structure as an efficient electrocatalyst toward the oxidation of methanol to produce formate. By a simple ultrasonic acid treatment and air oxidation at room temperature, an inert NF was converted to NiO/NF as a catalytically active electrode due to the uniform NiO nanosheet array that was rapidly formed on the surface of NiO/NF. In alkaline electrolytes containing methanol, the as-prepared NiO/NF catalysts exhibited a lower methanol oxidation reaction (MOR) potential of +1.53 V vs RHE at 100 mA cm −2 compared to that of inert NF samples. The difference in potentials between the E MOR and the E OER at that current density was found to be 280 mV, indicating that methanol oxidation occurred at lower potentials as compared to the oxygen evolution reaction (OER). We also observed that the NiO/NF could also efficiently catalyze the oxidation of CO without being poisoned by it. NiO/NF retained close to 100% of its initial activity after 20,000 s of methanol oxidation tests at high current densities above 200 mA cm −2 . Because of the simple synthesis method and the enhanced catalytic performance and stability of NiO/NF, this allows methanol to be used as an OER masking agent for the energy-efficient generation of value-added products such as formic acid and hydrogen.