wileyonlinelibrary.com Pt, Ir, and Ru, et al. are usually effective to boost the ORR or OER rate, [ 2,3 ] but their practical applications are severely limited by the prohibitive cost, scarce resource, and poor durability. Therefore, non-noble metal material and even non-metal material were explored for overcoming the limitation of the precious metal electrocatalysts for ORR and OER. [4][5][6] In particular, the bifunctional electrocatalysts for both OER and ORR reactions were highly desired for the unitized regenerative fuel cells (URECs), which can do the water electrolysis in regenerative mode and function in the other mode as a fuel cell recombining oxygen and hydrogen gas to produce electricity. Recently, Dai and co-workers [ 6 ] reported that the nitrogendoped carbon nanotubes (NCNTs) acted as an excellent electrocatalyst candidate with better electrocatalytic activity, long-term stability, and tolerance to crossover effect than the conventional Pt for ORR. Furthermore, the nitrogendoped carbon materials were found as the effi cient oxygen evolution electrocatalysts with comparable activity to those of iridium and cobalt oxide catalysts. [ 5 ] The N-doped carbon materials were with low cost, high catalytic activity, long durability, as well as abundant resource on earth, which were potential catalysts for oxygen electrochemistry and highly concerned recently. [ 5,7 ] The incorporation of nitrogen atoms into the carbon frameworks can effectively modulate the electronic structure of the surrounding carbon atoms and tune the local charge density distribution, [ 8 ] which results in the improvement of the chemical reactivity and subsequently promotes the catalytic performance. [ 9 ] In heterogeneous catalysis, the active sites of the catalysts are expected to be exposed at the surface which can be accessible to the reactants as much as possible in order to achieve high catalytic effi ciency. However, for most of routine NCNTs directly synthesized by chemical vapor deposition (CVD) growth and chemical doping, [ 6,10,11 ] the incorporated N atoms distributed uniformly in general, whereas the active sites induced by the dopant atoms in the inner walls of NCNTs were hardly accessible and consequently contributed to the catalytic property scarcely. Besides, the bamboo-like structure or the cup-stacked structure of the routine NCNTs render complex packing of graphene layers, which hinder the rapid electron The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play a decisive role for the effi ciency of fuel cells and metal-air batteries. The nitrogen doped carbon materials with low cost and long durability are potential catalysts to replace precious metal catalyst for oxygen electrochemistry; however, the unexposed active sites induced by the bulk dopant atoms are hardly accessible and consequently scarcely contribute to the catalytic property. In this study, carbon nanotubes (CNTs) are selected as the platform to demonstrate the potential of full exposure of 'active sites' at the surface. Nove...