<jats:title>Abstract</jats:title><jats:p>From the saponin of the stem barks of Dodonaea viscosa (L.) Jacq. (Sapindaceae) we have isolated the known genins R<jats:sub>1</jats:sub>‐barrigenol and Jegosapogenol and two novel prosapogenins R<jats:sub>1</jats:sub>‐barrigenol 21,22‐diangelate and Jegosapogenol 21‐(2,3‐dihydroxy‐2‐methylbutyrate),22‐angelate. Structures have been elucidated chiefly by spectroscopic means.