Nitrogen-doped carbon nanofiber webs (CNFWs) with high surface areas are successfully prepared by carbonization-activation of polypyrrole nanofiber webs with KOH. The as-obtained CNFWs exhibit a superhigh reversible capacity of 943 mAh g(-1) at a current density of 2 A g(-1) even after 600 cycles, which is ascribed to the novel porous nanostructure and high-level nitrogen doping.