We have successfully prepared PVP/LiCoO2 nanofibers using an electrospinning route. These fibers were composed of very small crystalline grains uniformly linked with an average size. After annealing of the above precursor fibers at 700 degrees C for 12 h, LiCoO2 nanofibers with 95 nm in diameter were composed of crystalline nanoparticles were successfully obtained. The morphology, crystal structure, and particle size of fibers has been characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD). The viscosities of solutions were measured with a LVDV Brookfield viscometer. Experimental results showed that the LiCoO2 with good crystalline and uniform diameter were obtained. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 154-160, 2011