The mitigation or elimination of methanol crossover for perfluorosulfonic acid fuel cell membranes has been investigated extensively for direct methanol fuel cell applications with the aim of increasing the electrochemical performance and enhancing the utilization rate of methanol. Self-assembly modifications by applying an oppositely charged polyelectrolyte to Nafion membranes were attempted in order to block or reduce methanol crossover while maintaining the other advantageous properties of Nafion membranes. It was reported that anionic polyallylamine hydrochloride (PAH) was the most efficient polyelectrolyte in reducing methanol crossover, and considerable cell performance was obtained even at a methanol feed concentration of 10 M.