A highly porous N self-doped carbon catalyst, with three dimensional morphology/structures and high surface area (810.8 m(2) g(-1)), is prepared through a pyrolysis procedure with polyacrylonitrile as the precursor, and zinc oxide (ZnO) as the templates/pore former. The catalyst exhibits excellent activity and stability towards oxygen reduction reaction (ORR) in alkaline medium, as well as outstanding methanol tolerance and stability. For our optimal catalyst PAC/ZnO-900, its half-wave potential is 26 mV more positive (0.859 V, vs. RHE) than that of commercial Pt/C catalyst (0.833 V, vs. RHE), and its current density at 0.88 V (vs. RHE) is almost twice as high as that of Pt/C catalyst (-1.922 and -0.957 mA cm(-2), respectively). It is found that the addition of ZnO plays a crucial role for the formation of catalysts' 3D porous structures and high ORR performance. With the addition of ZnO in precursor, the surface area of the catalyst is enhanced by 13 times, and the ORR activity is enhanced by 10 times. Also, pyrolyzing temperature seems to be another important factor significantly affected the structure and performance of the catalyst. (C) 2016 Elsevier B.V. All rights reserved.