Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in fuel cell electric vehicles applications. The further request of high-efficiency and cost competitive technology make high-temperature proton exchange membranes utilizing phosphoric acid-doped polybenzimidazole be favored because they can work well up to 180 °C without extra humidifier. However, they face quick loss of phosphoric acid below 120 °C and resulting in the limits of commercialization. Herein UiO-66 derived carbon (porous carbon–ZrO), comprising branched poly(4,4′-diphenylether-5,5′-bibenzimidazole) and polyacrylamide hydrogels self-assembly (BHC1-4) membranes for wide-temperature-range operation (80–160 °C) is presented. These two-phase membranes contained the hygroscopicity of polyacrylamide hydrogels improve the low-temperature proton conductivity, relatively enable the membrane to function at 80 °C. An excellent cell performance of BHC2 membrane with high peak power density of 265 and 656 mW cm at both 80 and 160 °C can be achieved. Furthermore, this membrane exhibits high stability of frequency cold start-ups (from room temperature to 80 °C) and long-term cell test at 160 °C. The improvement of cell performance and stability of BHC2 membrane indicate a progress of breaking operated temperature limit in existing PEMFCs systems.