A three layer membrane (TLM) of polybenzimidazole/graphite oxide/polybenzimidazole (PBI/GO/PBI) has been fabricated as an electrolyte for intermediate temperature polymer exchange membrane fuel cells (IT-PEMFCs). The membrane is prepared by encapsulating a GO layer with two single PBI membranes via a layer-by-layer procedure and subsequently imbibed with phosphoric acid (PA). The TLM exhibits a lower swelling ratio than that of the pristine PBI membrane at the same PA loading time. The mechanical strength of the TLM could reach 28.6 MPa at 150 °C, significantly higher than that of a PBI membrane (12.2 MPa). The TLM is loaded with a PA amount of 2.23H3PO4 molecules per repeat unit (PRU), which provides a proton conductivity of 0.0138 S cm−1 at 150 °C. The three layer structure promotes a membrane for PEMFCs with lower PA leakage and material corrosion. The fuel cell performance based on TLM exhibits a peak power density of 210 mW cm−2 at 150 °C.