Diethyl ether was widely used as an anesthetic agent in many countries in the second half of the 19th century and the first half of the 20th century. For this reason the majority of lethal cases involving diethyl ether reported during this period were associated with anesthesia. We present a case of asphyxial death by plastic-bag suffocation with additional detection of diethyl ether in autopsy specimens. Autopsy initially failed to reveal the cause of death. Macroscopic and microscopic findings as well as subsequent toxicological examination procedures and results are pointed out in the present case report. Headspace gas chromatography with flame ionization detection (HS-GC-FID) coupled with gas chromatography/mass spectrometry (GC-MS) proved to be the method of choice for fast and reliable analysis of unknown highly volatile substances (other than blood alcohol). In this case the detection of diethyl ether in autopsy specimens led to further investigations by the police at the death scene. During these investigations a bottle bearing a diethyl ether label was found and confiscated, which proved the insufficiency of prior death scene investigation.In order to evaluate the case from every possible angle, in such cases, especially when plastic-bag suffocation is suspected, we strongly recommend the collection of postmortem specimens in gas-tight vessels as well as the presence of a forensic expert at the death scene.