Zirconia (ZrO2) inorganic ceramic nanofibers were produced using electrospinning of the poly(vinyl alcohol)/zirconium acetate as a precursor followed by calcinating and sintering to decompose the polymer and turn the metal salt (zirconium acetate) into the metal oxide. Characterization of the nanofibers, including polymer thermal decomposition, chemical and crystal structure, phase transformations, and fiber morphology were investigated by simultaneous thermal analysis (STA), thermomechanical analysis (TMA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM). The results showed that the polymer decomposition started at 250 degrees C and zirconia nanofibers with different phases (tetragonal and monoclinic) were obtained by the calcination of the precursor nanofibers at various temperatures between 500 degrees C and 1100 degrees C. The initially crystallized zirconia phase, which formed at 500 degrees C, was tetragonal and with increasing calcination temperature, zirconia nanofibers with increasing amount of monoclinic phase were formed. Consequently, at 1100 degrees C, the tetragonal phase disappeared and was transformed to the monoclinic phase of the zirconia completely. Increasing the calcination temperature caused the fiber average diameter decrease and grain growth took place due to the removal of the polymer and organic groups; neighboring grains sintered to each other and formed fibers with a high aspect ratio. At 1100 degrees C the grains size was about the same as the fiber diameter.