Zirconia nanofibers were fabricated from alcoholic solution containing zirconatrane and poly(vinyl pyrrolidone) (PVP) using electrospinning and sol-gel process with subsequent calcination process. A low-cost and facile route to synthesize zirconatrane complex, which can be further employed as alkoxide precursor for zirconia or doped zirconia via sol-gel technique, has been developed from the reaction of a very inexpensive and plentiful starting materials via the oxide one-pot synthesis (OOPS) process. Zirconatrane complex was directly synthesized from zirconium hydroxide, triethanolamine and ethylene glycol. The structure of resultant products was fully characterized using FTIR, 1H, 13C-NMR, elemental analysis (EA), and mass spectroscopy (MS). The PVP/zirconia composite nanofibers were electrospun and calcined at different temperatures. The as-electrospun and heat-treated PVP/zirconia composite nanofibers were characterized using TGA, XRD and SEM. After calcination of the as-spun composite fibers at 600oC for 5 h, zirconia nanofibers of about 190 nm in diameter having tetragonal structure were obtained. Increasing the calcination temperature resulted in the formation of zirconia fibers with ribbon-like morphology having an average width of 600 nm and thickness of 140 nm.