Mass spectrometry in both electron-impact and positive chemical ionisation modes has been used to elucidate the structures of the decomposition products of zopiclone after gas chromatography. A high-performance liquid chromatographic method has been developed for the determination of zopiclone in whole blood. After selective extraction (butyl chloride) the extracts are chromatographed on Spherisorb ODS-5 (5 microns) using dibasic ammonium phosphate-acetonitrile (40:60). The zopiclone is measured by ultraviolet detection with a limit of quantitation of 4 ng/ml. This method has been successfully applied to the determination of zopiclone in post-mortem blood. Zopiclone levels found in five post-mortem cases are presented.