Dendrobine is an important sesquiterpenoid alkaloid bearing the picrotoxane carbon skeleton isolated from the traditional Chinese medicine "Chin-Shih-Hu".Because of structural characteristics of fused polycyclic and seven contiguous stereocenters, and exhibiting analgesic, antipyretic activities, dendrobine has attracted a great deal of attentions from both synthetic organic chemists and medicinal chemists.Over the past 50 years, there has been a number of research reports on the pharmacological activities and chemical synthesis of dendrobine.This review summarizes the biosynthetic hypothesis and synthetic advances on dendrobine.