Electrospun poly(ether sulfone) (PES) membrane impregnated with Nafion (PES-N) have been developed for high-temperature polymer-electrolyte membrane fuel cell (HTPEMFC). The PES-N obtains highly thermal stability up to 430oC, which is higher than that of the commercial Nafion 212. The PES-N membrane shows a good proton conductivity of about 10-2 S cm-1 in a temperature range from 75oC to 120oC. The membrane-electrode assembly (MEA) with the PES-N membrane exhibits a current density of 1.697 A cm-2 at 75oC, and 0.813 A cm-2 at 110oC when the applied voltage is 0.6 V, whereas the MEA with the Nafion 212 membrane shows the current density of 0.647 Acm-2 at 110oC. The results suggest that the PES-N can be a good candidate for a polymer electrolyte membrane of the HT-PEMFC.