A three-dimensional porous nanostructure electrode composed of copper skeletons and platinum shells (NPC-Pt) was prepared by electroless plating for the first time. The electrochemical behavior of this electrode for electrocatalytic reduction CO2 in ionic liquid, 1-butyl-3-methylimidazoliumtetrafluoborate (BMIMBF4), had been studied by cyclic voltammogram and electrochemical impedance spectroscopy with a reduction peak at -2.24 V (vs. Ag) which was more positive 180 mV than that obtained on a pure platinum electrode. The electrolyses experiments were carried out in an undivided cell under mild conditions without any toxic solvents, catalysts and supporting electrolytes, affording the dimethyl carbonate in a good yield (81%). In addition, the current for the CO2 reduction at NPC-Pt electrode was stable, with a higher current density and current efficiency (83%). Moreover, current efficiency remained after reusing it for five times. (C) 2012 Elsevier B. V. All rights reserved.