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One-dimensional porous carbons bearing high surface areas and sufficient heteroatom doped functional-ities are essential for advanced electrochemical energy storage devices, especially for developing free-standing film electrodes. Here we develop a porous, nitrogen-enriched, freestanding hollow carbon nanofiber (PN-FHCF) electrode material via filtration of polypyrrole (PPy) hollow nanofibers formed by in situ self-degraded template-assisted strategy, followed by NH3-assisted carbonization. The PN-FHCF retains the freestanding film morphology that is composed of three-dimensional networks from the entanglement of 1D nanofiber and delivers 3.7-fold increase in specific surface area (592 m2·g-1) com-pared to the carbon without NH3 treatment (FHCF). In spite of the enhanced specific surface area, PN-FHCF still exhibits comparable high content of surface N functionalities (8.8％, atom fraction) to FHCF. Such developed hierarchical porous structure without sacrificing N doping functionalities together enables the achievement of high capacity, high-rate property and good cycling stability when applied as self-supporting anode in lithium-ion batteries, superior to those of FHCF without NH3 treatment.