The metal-free nitrogen-doped graphitic-carbon@graphene (Ng-C@G) is prepared from a composite of polyaniline and graphene by a facile polymerization following by pyrolysis for electrochemical oxygen reduction reaction (ORR). Pyrolysis creates a sponge-like with ant-cave-architecture in the polyaniline derived nitrogenous graphitic-carbon on graphene. The nitrogenous carbon is highly graphitized and most of the nitrogen atoms are in graphitic and pyridinic forms with less oxygenated is found when pyrolyzed at 800 °C. The electrocatalytic activity of Ng-C@G-800 is even better than the benchmarked Pt/C catalyst resulting in the higher half-wave potential (8 mV) and limiting current density (0.74 mA cm-2) for ORR in alkaline medium. Higher catalytic performance is originated from the special porous structure at microscale level and the abundant graphitic- and pyridinic-N active sites at the nanoscale level on carbon-graphene matrix which are beneficial to the high O2-mass transportation to those accessible sites. Also, it possesses a higher cycle stability resulting in the negligible potential shift and slight oxidation of pyridinic-N with better tolerance to the methanol.