In recent years Ceria based heterostructure composites are considered as one of the highest performing solid state ionic conductors, therefore we wanted to leverage the benefits of using these materials for high temperature Proton Exchange Membrane Fuel Cells (PEMFCs). In this study a Polybenzimidazole (PBI)/Ceria carbonate CHC (Ceria based heterostructure composite) membrane was prepared by drop casting method and tested as an electrolyte for a high temperature H2/Air PEMFC application in anhydrous condition. Inorganic composite of ceria and alkali metal carbonates (Li2CO3, Na2CO3) was prepared by solid state route to obtain Ceria carbonate CHC. X-Ray diffraction (XRD) study confirmed the formation of the heterostructure and their successful incorporation into the PBI membranes. Homogeneity of fillers inside the membrane was further verified by Energy Dispersive X-Ray Analysis (EDAX) and Scanning Electron Microscopy (SEM). 5wt% of inorganic powder induced inside the PBI fillers reduced the phosphoric acid uptake of composite membrane (∼17% less) compared to pristine PBI membrane, which ultimately resulted into a lower swelling and dimensional change of the composite membrane. Thermal robustness of the phosphoric acid doped composite and pristine PBI membranes was investigated by thermogravimetric analysis (TGA) which showed that the prepared membranes were gone under a less than 10% reduction in weight up till 200ºC, ensuring their validity of application in high temp PEM fuel cells. The added inorganic functionalities resulted in a slight increase in the proton conductivity of PA doped composite PBI membranes i.e., 42.3 mS cm-1 at 180 ºC while for pristine PBI membrane it is 36 mS cm-1 at same temperature. A single cell with composite PBI membranes outperformed a pristine PBI membrane resulted into a ∼120% higher peak power density i.e., 320.88 mW cm-2. The composite membrane also displayed the excellent durability and showed a less than 10-4 mV/h degradation in cell potential till 180 ºC.