Sodium azide (NaN3) is an inorganic matrix compound with a very high toxicity. Mechanism of action is not clarified, and it is assumed to interfere with the processes of oxidative phosphorylation. The acute intoxications with sodium azide are extremely rare. We described a case of 19-year-old man who was found dead. In the course of prosecution the empty container, with label "NaN3, 20 g", was found near the body. There were traces of white powder detected in the container. Azide ions were determined by derivatization, i.e. they were transformed to pentafluorobenzaldehyde azide compound. Analysis of the final extract after derivatization was performed by gas chromatography coupled with mass spectrometry GC/MS. The largest concentration of azide ions were determined in the stomach content and vitreous humour, and much less one in whole blood, urine and kidney fluid.