The composite fibers of polyvinyl alcohol (PVA) and zirconium (Zr) n-propoxide were produced by an electrospinning process using the mixed solution of PVA and sol of zirconium n-propoxide. Effects of process parameters, viz, applied voltage, needle to collector distance and flow rate, were studied on the composite fibrous morphology. Bead-free composite fibers, with fiber diameter ranging from 155 nm to 850 nm, were produced with different process parameters. The morphology of the fibers varies significantly with the heat treatment. Heat treatment of the composite fibrous mats results in the removal of PVA, which causes the surface rough while retaining the fibrous morphology. The XRD studies reveal that the structure of PVA free ZrO2 fibers is tetragonal. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.