Nanoporous Ni-Cu-P amorphous alloy (NP-NiCuP) and nanoporous Ni-Cu crystalline alloy (NP-NiCu) are prepared by the linear sweep voltammetry (LSV) etching of copper from the electroless Ni-Cu-P and Ni-Cu alloy coatings, respectively. The results of X-ray diffraction(XRD) analysis show that the nanoporous Ni-Cu-P alloy is amorphous structure. The scanning electron microscopy (SEM) analysis demonstrates the NP-NiCuP shows a 3-D bi-continuous porous structure with the pore size of 150-200 nm and the ligament size of around 100nm. Electrochemical performances are measured by cyclic voltammetry (CV) and chronoamperometry (CA). The results prove that the NP-NiCuP electrode exhibits higher the proton diffusion coefficient (D-0) of Ni(OH)(2) and surface coverage (Gamma*) of the redox species than those on smooth electroless Ni-Cu-P amorphous alloy (S-NiCuP) and NP-NiCu electrodes in alkaline solution obviously. Moreover, electro-oxidation of methanol suggests that the NP-NiCuP electrode holds higher anodic current density and lower onset potential than the S-NiCuP and NP-NiCu electrodes. Finally, the NP-NiCuP electrode has stable redox behavior and superior catalytic stability for methanol oxidation. (C) 2014 Elsevier Ltd. All rights reserved.