Phytochemical investigation of the whole plants of Dicranostigma leptopodum (Maxim) Fedde has led to the isolation of two quaternary protoberberine alkaloids 5-hydroxy-coptisine (1) and berberrubine (2). This type of alkaloids was isolated from the genus Dicranostigma for the first time and the new compound structure (1) was elucidated by various spectroscopic methods including 2D NMR techniques (gCOSY, HMQC and HMBC) and HR-ESI-MS. © 2014 Taylor & Francis.