Lipids are a broad group of naturally occurring molecules, which includes fats, oils, waxes, sterols, terpenes, fat-soluble vitamins, monoglycerides, diglycerides, phospholipids and others. Lipids have been widely used in human history and they are often present in archaeological finds. In particular, in the field of medicine and cosmetics, lipids have been employed as base in the preparation of unguents, salves and balms. The characterization of these products and their degradation products induced by ageing is important for an understanding of the ancient pharmaceutical techniques and to assess the state of conservation. 1 H-NMR and, for the first time, 31 P-NMR spectroscopy have been applied to the characterization of such compounds. By derivatization of the samples with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, it is possible to recognize, quantify and evaluate the degradation degree of lipids in archaeological unguent samples. With this new approach, lipids have been recognized in 17th-century archaeological ointments from the Aboca Museum. Moreover, severe hydrolysis and oxidation markers have been detected.