Controlling the growth of (001) lattice plane for orthorhombic niobium pentoxide is an effective method to enhance its electrochemical performance. Herein, the oriented Nb2O5@C nanorods with capsule structure which grows along the perpendicular direction to the (001) lattice plane are successfully fabricated by a hydrothermal method with a later heat treatment process. As an anode for Li-ion batteries, the oriented Nb2O5@C composite delivers an ultralong cycling stability of 200 mAh g−1 after 1000 cycles at 5 A g−1 and enhanced rate capability of 413 and 143 mAh g−1 at 0.1 and 5 A g−1 respectively, which are much better than those of Nb2O5 electrode. Further investigations reveal that the oriented Nb2O5@C composite shows lower charge-transfer resistance, higher Li+ diffusion coefficient and maintains a surface-controlled pseudocapacitive mechanism. The superior performances are ascribed to the synergetic effect of [001]-orientation, small Li+ diffusion lengths in the nanorods building flowers and capsule-nanostructure with uniform carbon coating.