The catalytic activity of well-nanostructured carbon, for example glassy carbon spheres, SWCNT, graphene, and graphite, has been demonstrated in the oxidative dehydrogenation (ODH) of butane to obtain olefins. The catalytic performance of the carbon samples was stable, with prolonged reaction time. The proportion of butenes in the product decreased as the reaction temperature increased, whereas selectivity for ethene and propene increased with increasing temperature. Pd-containing carbon nanofibers (CNF) had superior selectivity for butadiene formation than Pd free CNF catalyst. Carbon with graphitic structures was highly selective for propylene and butenes without severe combustion in ODH of butane.