Ultrafine apatite fibers were prepared by electrospinning of sol-gel precursor/poly( vinyl pyrrolidone) ( PVP) solutions followed by subsequent calcination. The as-clectrospun and calcinated fibers were observed under a scanning electron microscope and an optical polarizing microscope. Results show that the, morphology and the diameter of as-electrospun fibers strongly depend on the viscosity and the surface tension of sol-gel precursor/PVP solutions. After calcination, the smooth as-electrospun fibers shrink and the fiber diameter decreases because of the removal of the polymer. The chemical evolution upon the transformation of the precursor from a gel to the final apatite fibers was investigated by thermogravimetric -differential thermal analysis, X-ray diffraction, and Fourier transform infrared spectroscopy. It is thus suggested that the crystalline structure of the calcined fibers is largely influenced by the calcination temperature. After being calcined at 600 degrees C, the apatite fibers with a diameter of about 280 nm containing, beta-tricalcium phosphate were obtained.