Nitrogen-enriched porous carbon nanofiber networks (NPCNFs) were successfully prepared by using low-cost melamine and polyacrylonitrile as precursors via electrospinning followed by carbonization and NH3 treatments. The NPCNFs exhibited inter-connected nanofibrous morphology with a large specific surface area, well-developed microporous structure, relatively high-level nitrogen doping and great amount of pyridinic nitrogen. As free-standing new anode materials in lithium-ion batteries (LIBs), the NPCNFs showed ultrahigh capacity, good cycle performance and superior rate capability with a reversible capacity of as high as 1323 mA h g(-1) at a current density of 50 mA g(-1). These attractive characteristics make the NPCNFs materials very promising anode candidates for high-performance LIBs and, as free-standing electrode materials to be used in other energy conversion and storage devices.