L-Ascorbic acid (AA) was directly supplied to polymer electrolyte fuel cells (PEFCs) as an alternative fuel. Only dehydroascorbic acid (DHAA) was detected as a product released by the electrochemical oxidation of AA via a two-electron transfer process regardless of the anode catalyst used. The ionomer in the anode may inhibit the mass transfer of AA to the reaction sites by electrostatic repulsion. In addition, polymer resins without an ionic group such as poly(vinylidene fluoride) and poly(vinyl butyral) were also useful for reducing the contact resistance between Nation membrane and carbon black used as an anode, although an ionomer like Nation is needed for typical PEFCs. A reaction mechanism at the two-phase boundaries between AA and carbon black was proposed for the anode structure of DAAFCs, since lack of the proton conductivity was compensated by AA. There was too little crossover of AA through a Nation membrane to cause a serious technical problem. The best performance (maximum power density of 16 mW cm(-2)) was attained with a Vulcan XC72 anode that included 5 wt.% Nation at room temperature, which was about one-third of that for a DMFC with a PtRu anode. (C) 2007 Elsevier B.V. All rights reserved.