Three-dimensional interconnected nanoporous coppers (NPCs) were synthesized by the dealloying of Cu-Ti and Cu-Ti-Ni amorphous ribbons in dilute H2SO4 solution. The effects of glassy precursor composition on the morphologies of NPC were evaluated comprehensively. The specific surface area of the NPC samples prepared by dealloying Cu66Ti30Ni4 (28.735 m(2) g(-1)) and Cu68Ti30Ni2 (20.196 m(2) g(-1) >) amorphous alloys is much larger than that of the Cu70Ti30 (9.080 m(2) g(-1)), indicating that the addition of minor amount of nickel has a great influence on the microstructure of NPC. Then, NPC with different microstructures were applied in the electro-oxidation of methanol in alkaline media. Among three catalysts, the NPC dealloyed by Cu66Ti30Ni4 amorphous ribbon exhibited the highest electrocatalytic activity (anodic peak current density: 298 mA cm(-2), presence of 1 M CH3OH in 1 M KOH solution) toward methanol oxidation, which is attributed to the larger number of active sites on the surface.