Macroporous Pt and PtAu electrodes (MP-Pt and MP-PtAu) were prepared through galvanic replacement at macroporous Cu electrodes, which were formed by electrodeposition of Cu at Au-coated indium tin oxide (Au/ITO) electrodes covered with ordered arrays of polystyrene (PS) nanospheres (PS/Au/ITO) in N-butyl-N-methylpyrrolidinium dicyanamide room temperature ionic liquid (BMP-DCA RTIL). After dissolving the PS templates in tetrahydrofuran (THF),macroporous Cu electrodes (MP-Cu/Au/ITO; denoted as MP-Cu hereafter) were obtained. The surface of a MP-Cu was spontaneously replaced by Pt or Pt/Au when a MP-Cu was immersed in an aqueous solution containing H2PtCl6 or H-2 PtCl6/HAuCl4 to form the MP-Pt (actually, MP-Pt/Cu/Au/ITO) or MP-PtAu electrodes. The atomic ratios of Au in PtAu could be adjusted by changing the concentration of HAuCl4 in the mixtures of H2PtCl6/HAuCl4. The electrodeposition potential, the time of replacement reaction, the concentrations of H2PtCl6 and HAuCl4, and the content of surfactant, which influence the structure of macroporous electrodes, were investigated. The surface morphologies of these macroporous electrodes were characterized with scanning electron microscope (SEM). MP-PtAu electrodes showed the better performance than the MP-Pt electrodes on the electrocatalytic oxidation of ethanol in alkaline solutions. (C) 2012 Elsevier Ltd. All rights reserved.