Abstract: OBJCTIVE To search the ESI-MS(n) performance of tanshinone constituents in Radix et Rhizoma Salviae Miltiorrhizae and to establish its LC-MS(n) characteristic spectrums. METHODS Direct injection ESI-MS(n) has been used in the construction analysis of tanshinone ⅡA. Tanshinone constituents in Radix et Rhizoma Salviae Miltiorrhizae were studied by HPLC-MS(n). MS(n) was carried out on positive ion mode and HPLC was performed on a Zorbax SB-C18 column using gradient elution with a mixture of purified water and acetonitrile at the detection wavelength of 254 nm. RESULTS We got the proposed ESI-MS fragmention pathway of tanshinone constituents. By analyze of HPLC/ESI/MS(n) and HPLC/UV chromatograms, 11 characteristic peaks were determined. CONCLUSION Tanshinone constituents have similar ESI-MS(n) performance that can be used in the structure identification of tanshinone compounds. HPLC-MS (n) is a useful tool for a special identification of tanshinone constituents in Radix et Rhizoma Salviae Miltiorrhizae.