Methods and cells are provided for electrochemically oxidizing methane to formate, in which methane supplied to an alkaline aqueous anolyte medium comprising hydroperoxyl anions is brought into contact with an oxidation catalyst anode. The oxidation catalyst may include CuFe oxide catalytic centres supported on a nickel substrate. An anodic current supplied to the oxidation catalyst in the anolyte medium electrolytically oxidizes methane to formate.