A novel biomass-based nitrogen-doped free-standing fused carbon fibrous mat was fabricated from lignin-polyethylene oxide (PEO) (90:10) blend via electrospinning followed by carbonization and thermal annealing in the presence of urea. The morphology and structure of the carbon fibers were characterized by field-emission scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis, and their electrochemical properties were investigated for the first time as anode in lithium ion batteries (LIBs). The fused carbon fibers without nitrogen doping exhibited high specific capacity up to 445 mA h g(-1) at a current density of 30 mA g(-1) (comparable to polyacrylonitrile (PAN) derived carbon nanofibers) and good cyclic stability at different current rates. After thermal annealing in the presence of urea, the charge capacity was further improved to as high as 576 mA h g(-1) and still maintained a good capacity of about 200 mAh g(-1) even at a high current rate of 2000 mA g(-1). This research demonstrates the great promise of lignin-derived nanocarbon materials for applications in energy storage systems.