Chitosan is considered one of the most promising materials for polymer electrolyte membrane fuel cells (PEMFC) due to the high manufacturing cost of the commercial polymer electrolyte membrane (PEM). In this study, chitosan (C-1), chloroacetate chitosan (CCS-21), epoxidized natural rubber (ENR-41), chitosan blended with ENR (CE-6 and CE-7), and chloroacetate chitosan blended with ENR (CCE-26 and CCE-27) based membranes were prepared by solution casting technique and crosslinked with acid and base. The Fourier transform infrared (FTIR) spectroscopy results showed improvements in their peaks, and the atomic force microscopy revealed that the blended membranes had a higher surface roughness than the other membranes. The optical contact angle (OCA) showed that the C-1 had the highest contact angle, while the ENR-41 had the least contact angle. From the electrical measurements, the CCS-21 gave the highest capacitance, conductance, and conductivity. The CE-7 showed the highest resistance and resistivity while ENR-41 showed the highest dissipation factor and dielectric constant. Taken together, CE-7 showed the most suitable characteristics which makes it suitable for use as a PEM.