Abstract Analytical strategies involving supercritical fluid extraction (SFE) from environmental matrices in tin, mercury, lead and arsenic speciation studies are presented. A combination of solid-phase extraction followed by SFE has been developed for the extraction of a variety of alkyl- and aryltin compounds from aqueous matrices. The method is successful for all the analytes if derivatisation is performed on the aqueous phase before the extraction. In situ derivatisation reactions prior to SFE with CO2 are discussed, together with the effects of modifiers (HCO2H, AcOH, or methanolic HCl) or complexing agents on the efficiency of extraction of organotins from solid matrices (i.e., aqueous, soil, sediment and biota). Carbon dioxide modified with AcOH provides the most successful procedure for the extraction of organotin compounds from sediment and biota. The method has been validated with certified reference materials for the butyltin content in sediments, and has been applied to the certification campaigns for butyl- and phenyltin content in sediment and biota carried out within the framework of the Standards, Measurements and Testing of the European Union. Therefore, this work updates a previous overview which only covered until 1993 the extraction and chromatography of organotin compounds using supercritical fluids [J.M. Bayona, Y. Cai, Trends Anal. Chem. 13 (1994) 327]. In addition, analytical strategies for the speciation of mercury, lead and arsenic from environmental matrices are presented for the first time.