Dual porous structures are observed for the first time on a metallic Cu surface underneath anodic Cu oxide by the application of an anodizing voltage to Cu in oxalic acid. The as-prepared porous Cu surface contains macropores of less than 1 μm diameter and mesopores of about tens of nanometers diameter with circular shapes. The size and density (number of pores/area) of the macropores are dependent on the applied voltage. It is likely that the localized dissolution (corrosion) of Cu in oxalic acid under the anodizing voltages is responsible for the formation of the mesopores, and the combination of a number of the mesopores might create the macropores, especially under a relatively high anodizing voltages or a prolonged anodizing time. The variations of pore structure (especailly macropores) with applied voltage and time are reasonably explained on the basis of the proposed mechanism of pore formation.