Ultra-thin fibers of zinc oxide (ZnO) were prepared by sol-gel processing and the electrospinning technique using poly(vinyl acetate) and zinc acetate as precursors. The fibers were characterized by thermogravimetric analysis, scanning electron microscopy, Fourier-transfer infrared, and X-ray diffraction, respectively. The results showed that the diameter of the precursor fibers increased with increasing zinc acetate content, and the size of the inorganic ZnO nanofibers decreased obviously as the calcining time increased.