An on-line method, with a purely aqueous mobile phase, has employed linked superheatedwaterextraction and superheatedwaterseparation for the analysis of triazineherbicides in spikedcompostsamples. After the superheatedwaterextraction, a X-Terra solid-phase trap was used to collect and focus the extracted analytes. The trapped analytes were then released by thermal desorption and passed directly to a superheatedwater chromatographic separation using a PGC column. Two clean-up steps (prior to extraction and separation) were included to remove most of the interfering matrix components. The effects of the sample matrix and the extraction temperatures on the recovery of the triazines were investigated. Despite some thermal degradation of the chloro-triazines during the SWE, the on-line SWE–SWC method was sensitive and rapid. The coupled method could potentially reduce costs and labour and by using only water in every stage is compatible with the concepts of green chemistry.