The catalytic activity of modified carbon powder (Vulcan XC-72R) for oxygen reduction reaction (ORR) in an air-breathing cathode of a microbial fuel cell (MFC) has been investigated. Chemical modification was carried out by using various chemicals, namely 5% nitric acid, 0.2 N phosphoric acid, 0.2 N potassium hydroxide and 10% hydrogen peroxide. Electrochemical study was performed for ORR of these modified carbon materials in the buffer solution pH range of 6–7.5 in the anodic compartment. Although, these treatments influenced the surface properties of the carbon material, as evident from the SEM-EDX analysis, treatment with H2PO4, KOH, and H2O2 did not show significant activity during the electrochemical test. The HNO3 treated Vulcan demonstrated significant ORR activity and when used in the single-chamber MFC cathode, current densities (1115 mA/m2, at 5.6 mV) greater than those for a Pt-supported un-treated carbon cathode were achieved. However, the power density for the latter was higher. Such chemically modified carbon material can be a cheaper alternative for expensive platinum catalyst used in MFC cathode construction.