<p>In this study, carbon-coated porous nanofibers were prepared via electrospinning and the performance of Li[Ni<sub>0.93</sub>Co<sub>0.07</sub>]O<sub>2</sub> (NC) synthesized by electrospinning (E-NC) and co-precipitation (C-NC) was compared. E-NC had a discharge capacity of 206 mAh g<sup>−1</sup> at 0.1C (17 mA/g), which is 10% higher than that of C-NC (189.2 mAh g<sup>−1</sup>). E-NC shows a high-rate performance of 118.32 mAh g<sup>−1</sup> (61.7%) at 5C (850 mA/g), which is 50% higher than that of C-NC (78.22 mAh g<sup>−1</sup> = 45.7%). Charge transfer of the carbon-coated porous nanofiber E-NC decreased by 35% compared to C-NC after 20 cycles as observed using electrochemical impedance spectroscopy. The results of this study show that the nanofiber structure with carbon coating shortens the Li-ion diffusion path, improves electrical conductivity, resulting in excellent rate performance.</p>