The applicability of a composite composed of polydimethylsiloxane (PDMS) and poly(vinyl alcohol) (PDMS/PVA) as coating sorbent for SPME fibers is demonstrated here. Fused silica (FS) fibers were coated with PDMS/PVA composite through a sol-gel process, using methyltrimethoxysilane as reticulating agent. The chemical and physical properties of the sol-gel PDMS/PVA composite were determined by infrared spectroscopy and thermogravimetric analysis. Electron scanning microscopy of the prepared fibers, showed that the coating obtained was highly microporous, having a thickness of approximately 5 microm. The fibers were tested for the headspace extraction of several organic compounds (o-xylene, naphthalene, ethyl caprate, p-chlorotoluene and PCB) prior to gas chromatographic analysis. The extractive capacity of the PDMS/PVA coating was found to be superior to that of pure conventional PDMS fibers.