The methanol distribution and electroosmotic drag in hydrated poly(perfluorosulfonic) acid electrolyte membrane are studied using molecular dynamics simulations under various electric fields applied. The results indicate that the methanol molecules are preferentially distributed near the hydrophobic PFSA backbones with their methyl groups in contact with the fluorine atoms and their hydroxyl groups pointing to the hydrophilic subphase. As the hydroxyl groups of methanol forming hydrogen bonds, hydroxyl groups are more likely to accept hydrogen atoms than to donate hydrogen atoms. The calculated methanol diffusion coefficient is in good correspondence with experimental values, and the electroosmotic drag coefficient for methanol is much smaller than that of water molecules.