Bi-functional catalysts are used to solve the poisoning problem caused by carbon monoxide (CO) which is the intermediate of direct methanol fuel cells (DMFCs). Flower-like vivianite (Fe-3(PO4)(2)center dot 8H(2)O) spheres with diameter around 10 mu m are originally used as supports of Pt to form bifunction catalysts. The cyclic voltammetry in 1 M H2SO4 indicates that the electrochemical surface area (ECSA) of Pt reduced on as-prepared vivianite (Pt/Vi) was 105, greater than 91 m(2) g(-1) for the commercial Pt/C. Besides, Pt/Vi reveals the less CO poisoning effects, including the greater mass activity in methanol oxidation and the lower onset potential in CO-stripping than Pt/C. These excellent performances on electrolyzes are related to the chemical state of Fe3+ and the coexistence of Pt-0 and Pt2+ in Pt/Vi. The former activates the water and yields Fe-OHads at lower potential and the latter may offer an easy way of electron transition. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.