Through sol-gel processing and electrospinning technique, extrathin fibers of poly(vinyl alcohol) (PVA)/lithium chloride/manganese acetate composite fibers were prepared. After calcination of the above precursor fibers at 600 degrees C, the spinel lithium manganese oxide (LiMn2O4) nanofibers, with a diameter of 100-200 nm, were successfully obtained. The fibers were investigated by TG-DTA, XRD, FT-IR, and SEM, respectively. The results showed that the crystalline phase and morphology of the fibers were largely influenced by the calcination temperature.