Gold wire was coated with polypyrrole (PPY) by electropolymerization and used as a solidphase microextraction (SPME) fiber. The adsorptive property of the coating was modified by doping with tetrasulfonated nickel phthalocyanine (NiPcTS). The efficiency and reliability of this fiber was investigated for the extraction of BTEX compounds from the headspace of water samples. Monitoring of extraction efficiency was performed by capillary GC-FID. Effects of several factors such as electropolymerization time, salt addition, exposure time and stirring speed on extraction efficiency were studied. The calibration graphs were linear in the range of 0.06 to 50 ng mL)1 and the detection limits for BTEX compounds were 20–50 pg mL)1. Comparing the results obtained using these fibers with results reported in the literature with polydimethylsiloxane (PDMS) fibers shows that under optimum conditions, the detection limits are comparable.