Two types of membranes, the sulfonated PEEK-WC (poly(oxa-p-phenylene-3,3-phthalido-p-phenylene-oxyphenylene) (SPWC) and Krytox-Si-Nafion (R) (KSiN) composite membranes are proposed for DMFC applications. The properties based on water uptake, ion exchange capacity, proton conductivity, gas permeability, thermal stability and methanol crossover are summarized. The comparative Studies on SPWC and Nafion (R) 117 membranes clarify us that the amorphous sulfonated PEEK-WC polymer shows thermal and mechanical stability with less methanol flux and gas permeability. The membrane also exhibits the increase in water uptake, ion exchange capacity and proton conductivity as sulfuric acid doping agent concentration was increased. The KSiN is unique in term of its miscible hybrid structure of silica particles modified with Nafion (R) structured Krytox 157 FSL chain (KSi) and Nafion (R). Based on the KSiN membranes with different KSi content, it was found that when KSi content increased, the reduction of gas permeability, methanol crossover and thermal stability are improved. The composite membrane performs the proton conductivity in the wide range of high temperature (60-130 degrees C).