This paper reports on the performance of directmethanol fuel cells (DMFCs) with the blend membranes of sulfonated polyether ether ketone (SPEEK)/ polyvinylidene fluoride (PVDF) as the electrolyte. The characteristic properties of the SPEEK/PVDF polymer membranes were investigated using thermo gravimetric analysis (TGA), scanning electronmicroscopy (SEM), and the AC impedance method. The blend shows good thermal and mechanical properties and appreciable ionic conductivity. Though the ionic conductivity decreased with increasing content of PVDF, there is an improvement in themechanical properties with the introduction of PVDF.As a result, the SPEEK/PVDF blends appear to be a good candidate as electrolytes for applications in DMFC. The performances of the membraneelectrode assembly (MEA) in DMFC, using the blend membranes of various percentages of PVDF (2-10%) were evaluated by single cell test and the maximumcurrent density of 350 mA/cm2 is observed around 0.25 V.