The roots of Rauwolfia volkensii yielded 26 alkaloids comprising five main groups--sarpagan, akuammicine, heteroyohimbine with derived oxindole and anhydronium bases, yohimbine with 18-hydroxy-yohimbine and its derived esters, and dihydroindole alkaloids. The principal alkaloids were ajmaline (0.08 per cent) and reserpiline (0.15 per cent), and the reserpine yield (0.0007 per cent) was very low.