The purpose of this study is to demonstrate some helpful postmortem biochemistry applications to highlight the value of this field and to reaffirm the need of conducting biochemical investigations as a crucial step in the autopsy procedure. In five case reports, diabetic ketoacidosis in an adult with multiple psychoactive drugs present and no history of diabetes, fatal flecainide intoxication in a poor metabolizer with impaired renal function, diabetic ketoacidosis with severe postmortem changes, primary aldosteronism with intracranial haemorrhage, and severe postmortem changes in hypothermia are all discussed. The cases discussed in this article serve as illustrative examples of the significance of postmortem biochemistry investigations. These investigations may yield important data that is useful in determining the cause of death in routine forensic casework or contribute to understanding the pathophysiological mechanisms involved in the death process.