Seven novel saponins were isolated from a bark extract of Quillaja saponaria Molina. the compounds were characterized, using mainly NMR spectroscopy, mass spectrometry and chemical methods, as quillaic acid substituted at C-3 with oligosaccharides consisting of various compositions of D-glucuronic acid D-galactose, D-xylose, and L-rhamnose and at C-28 with complex oligosaccharide structures consisting of various compositions of D-xylose, L-rhamnose, D-apiose and a branched 4-O-acetyl-D-fucose residue.