Highly conducting graphene/polyaniline (GN@Pani) nanocomposite was prepared by the in-situ oxidative polymerization of aniline in the presence of GN and the surfactant, cetyltrimethylammonium bromide (CTAB). The micellar structure of CTAB assisted both, the formation of GN@Pani tubules and the dispersion of GN. Sheet-like GN was distributed uniformly in the Pani matrix, leading to high electrical conductivity because of the π-π interactions between Pani and GN. Studies of the thermoelectrical behavior using isothermal and cyclic aging techniques showed that GN@Pani possessed a high combination of electrical conductivity and thermal stability, even beyond 150°C. GN@Pani was used as cathode active material in microbial fuel cells, and showed an enhanced power density and cell voltage, leading to better catalytic performance compared to plain carbon paper.