A proton exchange membrane for fuel cell application consists of modified chitosan/PEO doped with different weight percentage of HPA acids cross-linked by sulfosuccinic acid. Modifying the chemical structure of the chitosan by means of sulfonation, which was successfully synthesized by direct sulfonating reagent 1,3-propane sultone, chemical structure and thermal stability of the membrane were characterized by FTIR and TG analysis. Further the membrane was characterized by XRD, SEM, AFM and impedance analysis. The results shows that the structure of the composite membranes becomes more compact compared with undoped membranes due to interaction between the sulfonic acid groups and amine groups. This could lead to increase the conductivity and reduce the excess swelling of the membrane. From all the results, these biodegradable and low-costs composite membrane was tested in the single-cell proton exchange membrane fuel cell and it predicts that chitosan-based electrolytes are promising material for fuel cell application.