We report here a facile electrochemical method on simultaneous fabrications of nanoparticles and three-dimensional (3D) porous films of Pb or Sn by a highly cathodic polarization of pure metals in a NaOH solution. The nanoparticles produced from the formation and decomposition of unstable metal hydrides were assembled into 3D porous structures with a hydrogen bubble template. The two 3D porous metal films exhibited a high electrocatalytic activity toward the electroreduction of oxalic acid. Moreover, the two 3D porous oxide surfaces of Sn and Pb prepared by air exposition and by electro-oxidation of the porous metal films of Sn and Pb, respectively, showed superhydrophobicity.