(1 - x)SiO2-(x)ZrO2 (x = 0.1, 0.2) composite fiber mats were prepared by electrospinning their sol-gel precursors of zirconium acetate and tetraethyl orthosilicate (TEOS) without using a polymer binder. The electrospun composite fibers were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and mercury porosimetry. The composite fibers having a tetragonal crystalline ZrO2 were obtained by calcining the electrospun composite fibers at high temperatures. The results show that the structure and crystallization of ZrO2 in the composite fibers can be controlled by sinterincy temperature, while the porosity and morphology of the fiber mats did not depend on the sintering temperature.