Organometal compounds of tin, mercury and lead were simultaneously determined in environmental water and sediment samples by CGC-ICPMS. Instead of classical liquid/liquid extractions, solid phase microextraction was used as sampling technique. In this method, the organometallic compounds arein situ derivatised in the aqueous phase and simultaneously extracted onto a polydimethylsiloxane fiber, so that organic solvents are no longer necessary. The sorbed organometals are subsequently released from the fiber in the GC injection liner by thermal desorption. By sampling from the headspace, only the species of interest are sampled and no interfering matrix components are coextracted. With this new method, derivatisation, extraction, preconcentration and injection into the GC takes only 10 min with a minimum of handling steps. Owing to the very low detection limits (0.13–3.7 ng/1 as metal) only small sample amounts (25 ml of water, 0.5 g of sediment) are needed for one analysis. Finally, SPME is an inexpensive sampling technique that can be used with standard split/splitless injection systems.