Three spectrometric methods, that is, spectrofluorimetry (SF), atomic absorption spectrometry with electrothermal atomization (ET-AAS), and atomic fluorescence spectrometry with hydride generation (HG-AFS) were used for the determination of total selenium in biological samples taken from postmortem material in a case of acute selenium compound poisoning. The precision of the SF, ET-AAS, and HG-AFS methods (RSD, n=10) was found to be in the ranges of 10.0-15.0, 3.0-6.0 and 1.0-1.5%, respectively, and the detection limit was 10.0, 4.0, and 0.1 μg/L of Se, respectively. In the case of HG-AFS, the analytical procedure takes less time and is less laborious than the other methods considered. The obtained results show the usefulness of the HG-AFS method as a supplementary analytical tool to the SF and ET-AAS methods with respect to the determination of selenium as well as the possibility of using this method as a primary one in forensic toxicology practice.