| Summary: | Oleogum resins of the genus <i>Commiphora</i> have been used in traditional medicines for centuries. More than 200 <i>Commiphora</i> species exhibit highly variable phytochemical compositions. A novel highly selective, sensitive, accurate HPLC-MS/MS method was developed and validated to quantify five characteristic phytosteroids and furanosesquiterpenoids, namely (<i>E</i>)-guggulsterone, (<i>Z</i>)-guggulsterone, curzerenone, furanoeudesma-1,3-diene, and myrrhone. The resulting contents and additionally GC analysis were used to classify and differentiate <i>Commiphora</i> oleogum resins of the species <i>C. myrrha</i>, <i>C. erythraea</i>, <i>C. mukul</i>, <i>C. holtziana</i>, <i>C. confusa</i>, and <i>C. kua</i>, as well as unspecified resins. Interestingly, a <i>Commiphora</i> sample from Ogaden, Ethiopia, comprised 446 ng/mg guggulsterones presumed to be unique to <i>C. mukul</i> from the Indian subcontinent. However, <i>Commiphora</i> from Ogaden differed considerably from <i>C. mukul</i> in respect to guggulsterones isomer’s ratio. Moreover, the cytotoxicity of <i>Commiphora</i> extracts, essential oils, botanical drugs containing <i>Commiphora</i>, and pure compounds against the epidermoid carcinoma A431, malignant melanoma RPMI-7951 and SK-MEL-28 cells was investigated in vitro. Thereby, especially <i>C. mukul</i> extract and <i>C. myrrha</i> essential oil exhibited high cytotoxicity against skin cancer cells with IC<sub>50</sub> of 2.9–10.9 µg/mL, but were less toxic to normal keratinocytes. In summary, <i>Commiphora</i> oleogum resins and its phytochemicals warrant further investigation aiming at chemotaxonomical classification as well as application in skin cancer treatment.
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