A polypyrrole (PPy) coated polyester fiber was provided by chemically-deposition of PPy on the surface of polyester fiber in the electrolyte of FeCl3 (as an oxidant) and pyrrole as a monomer. The Scanning Electron Microscopy (SEM) was used for characterization of morphology, size and porosity of synthesized polymer. The seed like PPy particles (50-150 nanometers) are observed according to the SEM results. The PPy fiber was employed to extraction of volatile organic compounds (VOCs) in sesame samples as an extraction agent. An experimental design was utilized to optimize operational parameters that affect the analysis of VOCs in sesame samples using headspace solid phase microextraction (HSSPME) in the pre-concentration step. Some parameters including, extraction time and temperature were optimized. Gas chromatography-flame ionization detection (GC-FID) was used for separation, detection and quantitation of VOCs. Results show that PPy modified polyester fiber is provided fast and easy by chemical method and is suitable for the successful extraction of the VOCs from sesame samples.