The sapogenol constituents of leaves of Pittosporum tobira AIT. (Pittosporaceae) have been examined. On the basis of chemical and physicochemical evidences, three sapogenols obtained by acid hydrolysis of crude saponin have been shown to be R₁-barrigenol (II), 21β-angeloyloxy-3β, 15α, 16α, 22α, 28-pentahydroxyolean-12-ene (=21-O-angeloyl-R₁-barri-genol) (IV), 21β-angeloyloxy-3β, 16α, 22α, 28-tetrahydroxy-olean-12-ene (=21-O-angeloyl-barringtogenol C) (V) respectively. A₁-barrigenol (I) has not been detected in the total acid hydrolysate of saponin.