Atrazine and three of its metabolites (Deset [desethylatrazine], Met [desethyl-desisopropyl-2-hydroxyatrazine], 2-Hydroxy [2-hydroxyatrazine]) were extracted from three different environmental matrices: soils, sediments and plants. Standard extraction remained constant to allow intercomparison. The recovery of the target analytes varied significantly from one matrix to one another. An extraction performed with modified supercritical CO2 is compared to a classical solid-liquid extraction [SLE] with methanol: water (4∶1). SFE does not require the clean-up of the extract that classical methods usually do for any of the sample types. The method enables analysis of all target analytes. Although recoveries are generally good, lower recoveries are obtained for natural samples. Classical extraction gave better recoveries, but does not enable characterisation of metabolites, indeed, several clean-ups are needed to remove interfering coextraction products. Although SFE may give lower recoveries than traditional extraction method for atrazine, it is an accurate analytical method that allows quantification of polar pesticides with high reproducibility and specificity, avoiding coextraction of important quantities of the sample matrix.