Electrospinning of sol-gels has been used to produce zirconium-doped polymer microfibers from zirconyl chloride and poly(vinylpyrollidone) precursors. Calcination of these structures between temperatures of 370 degrees and 930 degrees C resulted in the formation of zirconia nanograined microfibers whose diameters ranged from 1200 to 800 nm at the higher temperatures and whose average grain size ranged from 9 to 33 nm. X-ray diffraction analysis revealed varying amounts of monoclinic and tetragonal zirconia present in the fibers and established how this varied with calcination temperature and time. The tetragonal phase was shown to be unstable and disappeared on heating the material beyond around 750 degrees C. The amount of zirconia yielded from the precursor material was measured and was found to be consistently greater than the theoretical yield. Average grain size within the microfibers increased with increasing calcination temperature and is effectively doubled when a 10 kPa pressure was applied. The effect of pressure also results in the creation of new crystal structures within the nanofibers and, as with traditional zirconia processing, the addition of impurity ions was found to stabilize the tetragonal phase.