A portable “diagnostic electronic nose” was used to study the composition of a mixture of volatile compounds emitted by the skin of the forearms in children with obesity and other associated metabolic disorders. Differences and features of the profiles of volatile compounds (primarily organic) of the skin on the left and right forearms in children with obesity and the dependence of the profile on food intake, drugs, concomitant diseases, and body characteristics were evaluated in hospital environment. More than 300 patient profiles were analyzed for 2 years, including the dynamics in profiles during repeated planned hospitalizations. The results suggest that the composition of the gas mixture of compounds emitted by the skin on the forearms can be analyzed and compared without preliminary separation or selection using an array of eight piezoelectric sensors of the “diagnostic electronic nose” device. We measured a correlation between the electronic nose data and the results of standard clinical laboratory tests. The parameters of a sensor array and clinical studies are closely related to each other in the levels of urea, alkaline phosphatase, and glucose. An approach based on scanning a volatile skin profile on the forearm for 3–6 min helps to rank children with obesity into groups associated with the socially significant diseases and conditions: “Normal,” “Obesity with a risk of development of type 2 diabetes mellitus,” and “Type 1 diabetes mellitus.” Using chemometric methods, we optimized the analytical procedure and specified research conditions and control points. The composition of the volatile skin metabolome on the right forearm, scanned on an empty stomach, is the most informative. The accuracy of the difference between the problem groups and the norm is 100%; the accuracy of the rank within pathological groups is 80%. The proportion of false assignments increases in the presence of inflammation in a body of any type. The potentials of the procedure were evaluated in a hospital environment.