Methanol crossover on the cathodes causes significant performance loss in direct methanol fuel cells, and the parasitic current induced by the electrochemical oxidation of methanol on the cathodes is believed to be the cause. Palladium cathodes are known to bear resistance to methanol but not platinum cathodes. By means of the density functional theory (DFT), the distorted molecular structure of the adsorbed methanol on platinum was revealed, and this distorted molecular structure indicates that platinum makes methanol has a tendency toward the elimination of the first hydrogen (involved in the first step of electrochemical oxidation of methanol) in electric neutrality, and loss of an electron can reinforce this tendency. However, palladium cannot distort the molecular structure of the adsorbed methanol, even in the loss of electron condition. The activation energies and the reaction energies calculated by means of DFT also show that after losing an electron, the elimination of the first hydrogen on platinum is more kinetically and thermodynamically favourable than that on palladium. These computational results can explain the experimental findings that no parasitic current is induced at palladium cathodes, but not at platinum cathodes; therefore, palladium cathodes have a methanol-resistance property. (C) 2015 Elsevier Ltd. All rights reserved.