The electrochemical coating technique was used for the preparation of a polypyrrole coating on a stainless-steel wire, and applied as a fibre for solid phase microextraction (SPME). The polypyrrole fibre was employed for analyzing four volatile aliphatic amines (ethylamine, propylamine, butylamine and pentylamine) in water by headspace SPME using gas chromatography-flame ionization detection (GC-FID). Results showed that this fibre coating is suitable for the successful extraction of the target analytes. The effects of the extraction parameters including exposure time, sampling temperature, salt concentration, and stirring rate on the extraction efficiency was optimized. Relative standard deviations (RSDs) was determined ? 4.3%. The correlation coefficient was satisfactory (r2 > 0.98) for the studied analytes. Detection limits were between 0.9 and 1.6 µg.L?1. Good recoveries (99-106 %) were obtained when spiked water and wastewater samples were analyzed.