Efficient metal-free carbon-based catalysts are of particular interest due to their unique electronic structure and compositional variability. Herein, petroleum-coke-based N,O-doped porous graphene (PG) was prepared as a preferred alternative to metal catalysts for catalytic oxidative reaction. Such a high specific surface area and heteroatom-rich structure promote high exposure of active sites, regulating the electron delocalization of materials effectively. In addition, the synergistic effect between N-doped and oxygen-containing functional groups is beneficial for the catalytic performance. As such, when employing the active PG as catalyst for the catalytic oxidative desulfurization (ODS), aromatic sulfur-containing compounds would be oxidized effectively and the sulfur removal in real diesel reached 84%. This work develops a facile approach for preparing heteroatoms co-doped porous graphene for aerobic catalytic ODS as well as an effective design idea for high value-added utilization of petroleum coke.