This study is concerned with electrochemical investigation of novel high-performance proton exchange membranes based on bio-functionalized montmorillonite and Nafion. It was found that the incorporation of 2 wt% BMMT into Nafion polyelectrolyte matrix results in significantly improved methanol-air fuel cell efficiency of 30% compared to 14% for Nafion(R)117, and about 23-times higher membrane selectivity.