Two sucrose esters, 3,6′-disinapoyl sucrose and tenuifoliside A were isolated from the n-butanol extract of the cortexes of Polygala tenuifolia Willd. by high speed countercurrent chromatography (HSCCC) in one or two steps. The two-phase solvent systems used were composed of chloroform-methanol-water (3:3.5:2 v/v) and ethyl acetate-n-butanol-ethanol-water (4:0.6:0.6:5). From 300 mg crude fraction, 3,6′-disinapoyl sucrose (40.1 mg) and tenuifoliside A (8.1 mg) were obtained at above 93% purity by HPLC analyses, and their structures were identified by IR, H NMR, C NMR, and MS spectra. Copyright © Taylor & Francis, Inc.