cited By 70 International audience Headspace solid-phase microextraction (SPME) followed by gas chromatography (GC) coupled to pulsed flame photometric detection have been investigated for the simultaneous speciation analysis of 14 organotin compounds, including methyl-, butyl-, phenyl-, and octyltins compounds. The analytical process (sorption on SPME fibre and thermal desorption in GC injection port) has been optimised using experimental designs. Six operating factors were considered in order to evaluate their influence on the performances of a SPME-based procedure. The evaluation of accuracy, precision and limits of detection (LODs) according to ISO standards and IUPAC recommendations has allowed the method to be validated. The LODs obtained for the 14 studied organotins compounds are widely sub-ng(Sn) l-1. The precision evaluated using relative standard deviation ranges between 9 and 25% from five determinations of the analytes at 0.25-125 ng(Sn) l-1 concentrations. The accuracy was studied throughout the analysis of spiked environmental samples. These first results show that headspace SPME appears really as attractive for organotins determination in the environment and the monitoring of their biogeochemical cycle. © 2003 Elsevier Science B.V. All rights reserved.