Flake-like LiCoO2 nanopowders were fabricated using electrospinning. To investigate their formation mech-anism, field-emssion scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were carriedout. Among various parameters of electrospinning, we controlled the molar concentration of the precursor and the PVPpolymer. When the molar concentration of lithium and cobalt was 0.45 M, the morphology of LiCoO2 nanopowders wasirregular and round. For 1.27 M molar concentration, the LiCoO2 nanopowders formed with flake-like morphology. Forthe PVP polymer, the molar concentration was set to 0.011 mM, 0.026 mM, and 0.043 mM. Irregular LiCoO2 nanop-owders were formed at low concentration (0.011 mM), while flake-like LiCoO2 were formed at high concentration(0.026 mM and 0.043 mM). Thus, optimized molar concentration of the precursor and the PVP polymer may be relatedto the successful formation of flake-like LiCoO2 nanopowders. As a results, the synthesized LiCoO2 nanopowder can beused as the electrode material of Li-ion batteries.