Diabetic ketoacidosis (DKA) is a lethal acute hyperglycemic complication of diabetes mellitus (DM) and it represents the initial manifestation of DM in about 15–20% of cases in adults and about 30–40% of cases in children. Postmortem diagnosis of DKA can only be made by applying thanatochemistry. Biochemistry applied postmortem is viewed with skepticism by many practitioners in the forensic field, completely lacking in many forensic services around the world, and especially in the national ones. This article aims to underline the importance of the postmortem application of biochemistry by reviewing the case of a person in the third decade of life who died suddenly at home due to diabetic ketoacidosis (DKA), whose autopsy was performed at an early PMI of approximately 24 h. Routine postmortem examinations (macroscopic, anatomopathological, and toxicological) could not establish a clear cause of death. When attention was turned to biochemical determinations (i.e., determination of glycated hemoglobin, glucose and ketone bodies (acetone, beta-hydroxybutyrate) in the blood, vitreous humor, and cerebrospinal fluid), the identified values clarified the thanatogenic mechanisms by establishing the diagnosis of DKA.