A procedure based on solid-phase microextraction (SPME) and gas chromatography-mass spectrometry, operating in the chemical ionisation mode, was developed and optimised in order to determine 10 triazines in water samples. Five different SPME fibers available for analysis [polydimethylsiloxane (PDMS) 100 microm, polyacrylate (PA) 80 microm, PDMS-divinylbenzene (DVB) 65 microm, Carbowax (CW)-DVB 65 microm, and Carboxen (CAR)-PDMS 75 microm] were tested, and PDMS-DVB was selected. To enhance the sensitivity of the SPME, variables affecting adsorption and desorption steps such as temperature, time, pH and ionic strength of the solution were optimised. Detection limits obtained were ranged between 2 and 17 ng l(-1), and precision values were below 8% for the selected PDMS-DVB fiber. The optimised method was applied to real water samples and no triazines were detected.