Acid doped polybenzimidazole membranes have emerged as an efficient electrolyte for high temperature polymer electrolyte membrane fuel cells (HTPEMFCs). The long term stability of polybenzimidazole membranes has been recognized as an important issue for commercial applications. Here, we report the oxidative degradation of polybenzimidazole membranes. The photoirradiation of poly(2,2'-ethylene-5,5'-bibenzimidazole) (PBIE) under accelerated photodegradation conditions was carried out by ultraviolet (UV) rays (λ > 300 nm) and characterized by Fourier transform infra red (FT-IR) spectroscopy, scanning electron microscopy (SEM), wide angle X-ray diffraction (WAXD) and contact angle measurements (CAM). The thermal properties of PBIE membranes were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) which revealed a lowering in thermal stability after photodegradation. FT-IR spectra revealed high absorbance in the carbonyl region in photoirradiated membranes whereas SEM showed nano structures / defects on the polymer film surface. CAM results showed enhancement in hydrophilic behavior and WAXD revealed increase in amorphous nature upon irradiation.