Nitrogen-doped carbon nanofiber webs (N-CNFWs) are prepared by direct pyrolyzation of polypyrrole (PPy) nanofiber webs at 600°C. The structure and morphology of N-CNFWs are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), Raman spectra and elemental analysis. Both the doped N content and the N existing type in carbon, change with the pyrolysis time. As anode material for lithium-ion battery, the N-CNFWs show high capacity and good rate capability. The reversible capacity is up to 668mAhg−1 at a current density of 0.1Ag−1 and 238mAhg−1 at 5Ag−1, which can be ascribed to the nanofiber structure and high nitrogen content.