Proton exchange membranes (PEMs) were prepared using Polybenzimidazole (PBI) copolymer synthesized from isophtalic acid and 3,3'-diaminobenzidine tetrahydrochloride dehydrate which produce a hydrophobic block. Hydrophilic polyamide (PA) blocks were synthesized from isophtalic acid and 4,4'-diamino-2,2'-biphenyldisulfonic acid. The addition of pentadecylphenol (PDP) forms supramolecular structures via phase separation (hydrophilic – hydrophobic). Composite membranes were also synthesized from polyamic acid and organoclay treated acid. The supramolecular sulfonated-PA / PDP / PBI membrane was tested in both the tangential and radial directions. Proton conductivity for this membrane is 3.3 x 10-3 S/cm in the tangential direction and 1.03 x 10-3 S/cm in the radial direction. In addition, proton conductivity for the composite membrane is 2.56.10-2 S/cm (80 oC).