Ordered here-array membranes of Pd were fabricated using two-step replication of anodic porous alumina. Electroless deposition of Pd on negative anodic porous alumina of polymethyl methacrylate resulted in a Pd hole-array structure with straight holes of nanometer dimensions. The controlled change of the size of hole openings in the Pd electrode was achieved after cathodic polarization in H2SO4, as a result of the deformation of the opening of the holes caused by hydrogen absorption at Pd.