We have successfully prepared nanostructured LiCoO 2 and LiMn 2 O 4 fibers using a novel high frequency electrospinning method. These fibers were composed of very small crystalline grains uniformly linked with an average size less than 100 nm. Scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV) were used to characterize their structures and electrochemical properties, respectively. These results suggested that a high frequency electrospinning was expected to be an effective method for the fabrication of inorganic composite fibers.