The present paper reviews the most relevant experimental data on miltirone, a diterpene pigment and one of the major active constituents with phenanthrene-quinone structure of the roots of Salvia miltiorrhiza. Radix Salvia miltiorrhizae Bunge (Labiatea, Laminaceae), a native plant in China, is listed in the Chinese Pharmacopoeia with the name of Danshen and used in Chinese folk medicine for the treatment of different pathologies. In fact, two types of major bioactive components in Dan-shen, including water soluble phenolic acids and lipophylic diterpenoid quinines, have the effectiveness in treating coronary heart disease, heart-stroke, cerebrovascular diseases, menstrual disorders, miscarriage, hepatitis and insomnia. Moreover, recent studies demonstrated the ability of different extracts of S. miltiorrhiza to suppress alcohol drinking in selectively bred Sardinian alcohol-preferring (sP) rats. Administration of miltirone to sP rats produced similar results, suggesting that it is the likely active constituent of S. miltiorrhiza responsible for the reducing effect of its extracts on alcohol intake. However, the study of S. miltiorrhiza components is very complex, therefore selective and efficient analytical methods are required to simultaneously determine their structures for further study of the pharmacological effects and to control the quality of the preparations in which are contained. Currently, there are many methods for the determination of phenolic compounds and diterpenes among which, highperformance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (LC-MS/MS) has been shown to be a powerful method for separation and identification of individual molecules in complex samples. In the proposal review, we will report an overview about the main results concerning the analysis of the main diterpenes constituents of S. miltiorrhiza in medicinal preparations and biological fluids, and our recent data on quantitative determination of miltirone in rat plasma.