Both structural and compositional modulations are important for high-performance electrode materials in energy conversion/storage devices. Here hierarchical-structure nitrogen-rich hybrid porous carbon capsules with bamboo-like carbon nanotube whiskers (N-CC@CNTs) grown in situ have been specifically designed, which combine the advantageous features of high surface area, abundant active sites, easy access to medium and favorable mass transport. As a result, the newly prepared N-CC@CNTs show highly efficient catalytic activity in oxygen reduction reaction in alkaline media for fuel cells, which not only outperforms commercial Pt-based catalysts in terms of kinetic limiting current, stability and tolerance to methanol crossover effect, but is also better than most of the nanostructured carbon-based catalysts reported previously. On the other hand, as an anode material for lithium ion batteries, the N-CC@CNTs obtained also exhibit an excellent reversible capacity of ca. 1337 mA h g(-1) at 0.5 A g(-1), outstanding rate capability and long cycling stability, even at a current density of 20 A g(-1). The capacity is the highest among all the heteroatom-doped carbon materials reported so far, and is even higher than that of many of the composites of metal, metal oxides or metal sulfides with carbon materials.