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N-doped graphene has been widely researched as metal-free electrocatalyst and electrode material of energy storage devices but the effect of heteroatom species and topographic defects on these applications was rarely reported. We successfully prepared dual (N, S) or ternary heteroatoms (N, S, P)-doped graphene by simple hydrothermal and then carbonization treatment. Compared to singly N doping, multiple heteroatom species dopant is beneficial to positively move onset potential, approach four electron catalytic pathway in oxygen reduction reaction (ORR) due to the synergistic effect. The emerging topographic defects induced by removing heteroatoms and oxygen at high temperature also act as efficient active sites for positively shifting onset potential. Meanwhile, the porous ternary heteroatoms-doped graphene possesses a good capacitive performance such as high gravimetric capacitance (196.4 Fg −1 at 1 Ag -1 ), high retained rate (92.7%), 98% retention over 2000 recycling. The excellent capacitive properties derive from large specific surface area (943.5 m 2 g -1 ), mesoporous structure, particularly the important role of abundant dopants of multiple heteroatom species. Therefore, we demonstrated the effect of heteroatom species and topographic defects on electrocatalyzing ORR and capacitive performance. [ABSTRACT FROM AUTHOR]