A solid-phase microextraction (SPME) method combined with gas chromatography with nitrogen-phosphorous and electron capture detection for the analysis of the pesticides terbumeton, metribuzine, isomethiozine, pyridafenthion and triadimenol in river water has been developed. For this purpose, polyacrylate and polydimethylsiloxane coated fibres have been utilised and the factors affecting throughput, precision and accuracy of the SPME method have been investigated and optimised. These factors include: matrix influence, adsorption time, pH, salt effect, desorption time, temperature and also the lapse of time between sampling and injection. The performed analytical procedure showed detectability ranging from 2.0 ng l(-1) to 3.0 microg l(-1) and precision from 1.9 to 27.7% (as relative standard deviation) depending on the pesticide, the fibre and the detector used. The results demonstrate the suitability of the SPME method to analyse these non-volatile pesticides in river water.