A new method for synthesizing alumina (Al2O3) nanofibers through the electrospinning method was reported. The spinning solutions of anhydrous aluminium chloride/polyvinylpyrrolidone (AlCl3/PVP), which were prepared by the sol-gel process of the mixture of AlCl3, PVP, ethanol and redistilled water, were electrospun to form AlCl3/PVP organic-inorganic hybrid fibers. Alumina nanofibers with average diameters of 100-800 nm were obtained by calcinations of the as-prepared fibers. The fibers were characterized by SEM, TG-DTA, FTIR, XPS and XRD. The results showed that with the increase of the concentration of spinning solution, the diameter of fibers also increased, and that the diameter of fibers decreased with the increase of the applied voltage and calcination temperature. The uncrystalline Al2O3, gamma-Al2O3 and alpha-Al2O3 were obtained after calcinations of about 5 h at 450, 900 and 1100 degrees C, respectively.