Two alternatives for the rapid simultaneous quantification of six sulfonylurea herbicides and five of their main degradation products in natural water are proposed. For concentration, the compounds were extracted on a polystyrene-divinylbenzene solid phase under pH and elution conditions that suppressed any hydrolysis. The eluates were analysed by liquid chromatography coupled to electrospray tandem mass spectrometry within 20 min. The whole method was validated and shown to give no hydrolysis artefacts. The application of off-line and on-line SPE of sulfonylureas enabled the 0.1 microg L(-1) and 1 ng L(-1) LOQ levels to be reached, respectively. The on-line SPE-LC-MS-MS method allowed the accurate quantitation of all sulfonylureas and three degradation products at 0.1 microg L(-1) or below in natural water, with an average repeatability of 8%.