The previous study on Picrasma quassioides has indicated that β-carboline alkaloids are a class of unique structure from it, and exhibit chemotaxonomic significance and characterize the species well, which could serve as valuable chemotaxonomic markers for the identification of Picrasma quassioide. This work describes 116 β-carboline alkaloids from P. quassioide, and we summarize the chemotaxonomic value of β-carboline alkaloids in P. quassioide for further study. Our results showed that Picrasma quassioide is a typical species of the Simaroubaceae family and an important source of β-carboline alkaloids with chemotaxonomic significance with Ailanthus Desf., Brucea J. F. Mill., Zanthoxylum, Quassia, and Eurycoma genera, together with the Rutaceae, Apocynaceae, Amaranthaceae, Rubiaceae, and Apiaceae family have some chemotaxonomic relationships. © 2023