This research focuses on the evolution of techniques in analyzing traces of odorous substances in human blood and sweat within law enforcement activities. The stages of development of methods for human identification through traces of odorous substances in sweat and blood (odor prints) are outlined. The authors describe the early stage (19th—early twentieth century) of employing service dogs in crime detection and investigation. The historical roots of contemporary techniques of olfactory human identification are demonstrated. The authors examined the process of developing methods for establishing the identity of a subject based on traces of odorous substances in their sweat and blood. Differences between the procedures of operational and investigative activities) “person and object selection” and forensic examination of human olfactory traces) are indicated. The shortcomings of the criminalistic odorology developed in the USSR in the 1960s are described. It shows how criticism by scientists—proceduralists of the initial tenets of criminalistic odorology- contributed to the formation of the contemporary methodology of olfactory examination of traces of odorous substances in human sweat and blood. The authors listed the main methodological features of the olfactory examination methodology applied in the Russian Federation. Methodological approaches to ensuring the reliability of results obtained in olfactory examinations are described. Compliance with the provisions of the olfactory examination methodology of traces of odorous substances in human sweat and blood with the requirements of the legislation of the Russian Federation for forensic examinations is demonstrated.