The polypyrrole (PPy) film was used for the selective extraction of trace levels of chloride, nitrite, and nitrate ions by solid phase micro-extraction (SPME). PPy film was electrochemically prepared from aqueous solutions of pyrrole and LiClO4 under N-2 atmosphere at constant potential of +0.80 V (versus Ag/AgCl). The anion uptake and release properties of the PPy film electrodes were examined under both open circuit and controlled potential conditions for prospective applications in electrochemically controlled solid-phase microextraction (EC-SPME). Applied positive and negative potentials facilitated the extraction and desorption of anions, respectively. Ions were desorbed into sample aliquot and were determined by ion chromatography (IC). The effect of uptake/release parameters, potential, time, pH of the uptake solution, on EC-SPME of anions was investigated. The method was validated using a standard reference material and tested for the determination of the ions in water samples. (C) 2008 Wiley Periodicals, Inc.