PtSn@Rh/C-HT catalysts were designed and synthesized by a two-step sequence synthesis: Rh was firstly deposited on the carbon support and then PtSn through microwave assisted polyol method, followed by the heat treatment (HT) in a reductive atmosphere. This well-designed process provided PtSn@Rh/C-HT with a desirable electrocatalytic activity towards the electrooxidation of ethanol as well as its intermediate products. Especially, for the acetic acid electrooxidation, PtSn@Rh/C-HT behaved quite different from Pt/C, PtSn/C, PtSn@Rh/C without heat-treatment, and PtSnRh/C fabricated through one-step method, without the characteristic peaks for hydrogen adsorption-desorption but significant oxidation current of acetic acid. This gives a platform for taking full advantage of the joint synergistic effect among Pt, Sn and Rh for direct ethanol fuel cell applications. (C) 2012 Elsevier B.V. All rights reserved.