Solid-phase microextraction (SPME) is a convenient and solvent free extraction method, which combines extraction, concentration and sample introduction in one step. Commercially available fibers are on the basis of fused-silica fiber coated with a thin layer of polymeric phases, similar to GC stationary phases. To improve the SPME technique, attention was attributed to the easy preparation of fibers, with convenient analytical characteristics. Metal wire coated with conducting polymers such as polypyrrole (PPY) have been attracted much attention in this area due to their potential technological applications and the relative ease of laboratory preparation. Several studies have revealed that the doping of PPY with some organic or inorganic compounds drastically changes the properties of the polymer. In this work, polypyrrole was modified by nickel phthalocyanine tetrasulfonated (NiPcTS) and was coated on the surface gold wire. This fiber was used for SPME of BTEX compounds from headspace of aqueous samples. Several factors such as adsorption and desorption time and temperature, fiber preparation and activation conditions were also screened in order to examine their effect on recovery. In the optimum conditions, the calibration graphs were liner in the range of 0.06-50 ng mL-1 and the detection limits for BTEX compounds were 20-50 pg ml-1.