LiCoO2 xerogel hollow nanofibers were first prepared by co-electrospinning the sol precursor, and the polycrystalline LiCoO2 hollow nanofibers were obtained after calcination of the xerogel fibers. The obtained hollow nanofibers made up of 20 similar to 30 nm nanocrystals were about 100 nm to several micrometers in outer diameter. The hollow nanofibers were detected by means of SEM, TEM, TG, DSC, FTIR, and XRD techniques.