This paper reports performance date for the direct methanol fuel cell (DMFC) with membrane electrode assemblies using modified poly (vinylidene fluoride) grafted the blended polystyrene sulfonated acid membranes (m-PVDF-g-PSSA) based on modified PVDF (poly vinylidene fluoride ) and the bended PSSA (polystyrene sulphonated acid). The membrane exhibited low methanol permeation coefficient, and good proton-conductivity. Furthermore, these materials have potentially lower methanol cross-over when compared to standard Nafion-type membranes. The membranes electrode assemblies were based on Nafion®-bonded carbon-supported catalyst: platinum/ruthenium for the anode and platinum for the cathode. The catalyst layer was coated directly on the treated membrane. To simulate the practical application, unit cell operates at room temperature and ambient pressure using liquid methanol and ambient air. A methanol solution is filled in the feed reservoir, and the cathode is exposed to ambient air. The cell performance of the self-breathing air DMFC, for short duration (<100h) testing, with the low cost membranes is superior to that of cells based on Nafion under identical operating conditions.