Novel polyaniline (PANI) electrodeposited in the presence of fluorinated organic acid was applied as a new conductive polymer-based solid-phase microextraction (SPME) fiber candidate. Polychlorinated biphenyls (PCBs) were selected as representative compounds. Improved temperature resistance (<500 degrees C) and satisfactory extraction efficiency were obtained by introduction of fluorinated organic acid. Extraction efficiency of novel PANI for PCBs was superior to common PANI (synthesized in sulfuric acid) and polythiophene, and comparable to commercial 30 microm PDMS but with thinner stationary, i.e. 10 microm. Quantitative determination of trace PCBs in water samples was carried out using this novel SPME fiber, coupling with selective gas chromatography-microelectron capture detector (GC-microECD). The proposed method provided a linear range of approximately three orders. The detection limits were 0.05 ng L(-1) for PCB 138, 153 and 180, and 0.1 ng L(-1) for PCB 28, 52 and 101, respectively. The method was successfully applied to the analysis of spiked surface water samples with the recoveries from 83.0 to 110.7%.