The technique of electrospinning was employed to fabricate uniform 1-D inorganic–organic composite nanofibers from alcoholic solutions containing polyvinyl pyrrolidone (PVP) and suitable aqueous precursors of yttrium and zirconium ions. Upon firing and sintering under carefully pre-selected time-temperature profiles, yttria-stabilized zirconia nanofibers retaining the original morphological features observed in the as-spun composition were obtained. X-ray diffraction was used to identify the crystalline fate of the final product. Analytical tools such as Raman spectroscopy and scanning electron microscopy (SEM) were employed to elucidate the pathway of ceramic phase formation and the systematic evolution of morphological features in the spun and the processed fibers. Several millimeters long, uniform YSZ nanofibers of high phase purity could be fabricated.