We report the synthesis and electrochemical performance of one dimensional NiO nanofibers by simple electrospinning technique and subsequently heat treated at 800 °C to yield single phase material. After the heat treatment, thickness and crystal size electrospun NiO is found ∼1 μm and 100 nm, respectively. The electrospun nanofibers are subjected to various characterizations such as X-ray diffraction with Rietveld refinement, scanning electron microscopy and transmission electron microscopy (TEM). Half-cell assembly is used to evaluate the Li-uptake properties and found maximum reversible capacity of ∼784 mA h g−1 at current density of 80 mA g−1 with operating potential of ∼1.27 V vs. Li. The test cell rendered good cycleability and exhibits capacity retention of over 75% of reversible capacity after 100 cycles. The conversion mechanism of metallic nanoparticles (Ni0) are validated though ex-situ TEM measurements. Rate performance studies are also conducted and delivered good cycling properties under such high current studies.