Hydrogen fuel cells proton exchangemembrane fuel cell (PEMFC) is currently still in development and commercialization. Several barriers to the commercialization of these Nafion membrane as electrolyte is its very sensitive to humidity fluctuation. Nafion must be modified by making a composite Nafion-SiO2-HPA to increase electrolyte resistance against humidity fluctuations during the cell used. Research carried out by mixing Nafion solution with Tetra Ethoxy Ortho Silicate (TEOS) and conductive materials is phosphotungstic acid (PWA) by varying the ratio of Nafion, TEOS and PWA. The membrane is produced by heating a mixture of Nafion, TEOS and PWA by varying the evaporation temperature, time and annealing temperature to obtain the transparentmembrane. The resultingmembrane was analyzed its physical, chemical and electrochemical properties by applying the membrane as electrolyte of PEMFC at various humidity and temperature of operation. The results showed that at low temperatures (30-90) °C and high humidity at 100 %RH, pure Nafion membrane is better than composite membrane (Nafion-SiO2-PWA), but at low humidity condition composite membrane is better than the pure Nafion membrane. It can be concluded that the compositemembranes of (Nafion-SiO2-PWA) can be used as electrolyte of PEMFC operated at low humidity (40 %RH) and temperature between (30-90) °C.