CaZrO3 (CZO) precursor fibers were prepared by sol-gel method and electrospinning technique from solutions which contained aqueous precursors of calcium and zirconium ions and polyethylene oxide. The crystallization of CZO fibers was a concurrent process with the decomposition of organics. The evolution process was characterized by Fourier transform infrared (FT-IR) and Raman spectra, thermogravimetry and differential scanning calorimetry (TG/DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The heat-conducting property and high temperature stability of fibers were characterized by the measurements of thermal conductivity and heating permanent linear change, respectively. The fibers were treated in NaOH solution at 80 degrees C to characterize the alkali resistance. The results showed that CZO fibers had the lower thermal conductivity than the other reported forms of CZO materials, and they possessed excellent stability up to 1100 degrees C with thermal shrinkage less than 1.2% and excellent corrosion resistance to alkalis. Hence, CZO fiber could be used as a suitable corrosion resistant refractory material for high-temperature thermal insulation.