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 (PO 4 ) 2 ·8H 2 O) spheres with diameter around 10 μm are originally used as supports of Pt to form bifunction catalysts. The cyclic voltammetry in 1 M H 2 SO 4 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 Fe 3+ and the coexistence of Pt 0 and Pt 2+ in Pt/Vi. The former activates the water and yields Fe-OH ads at lower potential and the latter may offer an easy way of electron transition.