Graphene base materials have received appreciable attention as substrate or nanocomposite with nonmetallic catalysts in alternative energy devices and technologies. The end application of iodine-doped (I-doped) graphene in fuel cells has been recently investigated as innovative nanomaterial for oxygen reduction reaction (ORR). Microscopic and spectroscopic techniques (SEM, FTIR, XRF, XPS) have been combined with structural investigation (BET) and electrochemical techniques for a comprehensive characterization of developed ORR catalysts. Moreover, the durability as ORR electrode have been evaluated in order to assess long-term performance. I-doped graphene was prepared by nucleophilic substitution of graphene oxide (GrO) by reduction with HI. The as-synthesized graphene with incorporation of iodine possesses unique structure revealing high surface area, mesopores and vacancies. The structural characteristics and their synergistic effects could not only improve the ions and electrons transportation but also limits the ohmic resistance. Thus the I-doped graphene exhibited superior electrochemical performances as well as long-term stability, which demonstrate that the I-doped graphene with great potential to be an efficient electrode material.