Thirty two alkaloids were isolated from the stem bark of Rauvolfia caffra and 28 were identified. The alkaloids represented corynane (3), strictamine (1), sarpagan (4), akuammicine (2), pleiocarpamine (1), indolenine (1), dihydroindole (6), peraksine (3), heteroyohimbine (2), hydroxyheteroyohimbine (2), oxindole (1), 2-acyl-indole (1), suaveoline (3) and yohimbine (2) types. The anhydronium base serpentine was detected but not isolated. The principal alkaloids were ajmaline and norajmaline (dihydroindoles), ajmalicinine and ajmalicine (heteroyohimbines), geissoschizol (E-seco indole) and pleiocarpamine and the heteroyohimbine derived alkaloids were predominantly normal configuration compounds. The biosynthetic and ethnopharmacological significance of the alkaloids is discussed.