Centrifugal partition chromatography (CPC) coupled with evaporative light scattering detection (ELSD) was applied to separate saikosaponins-a and -c preparatively from Bupleurum falcatum roots. The two-phase solvent system composed of ethyl acetate/n-butanol/methanol/water (15:1:3:15 by volume) was used to yield saikosaponins-a (36.1 mg) and -c (28.7 mg) from 370 mg of saponin-rich extract. The purities of isolated compounds were 96.6 and 97.3% for saikosaponins-a and -c, respectively. Structure identification of these compounds was accomplished by comparison of spectroscopic data of ESI-MS, 1H NMR, and 13C NMR with those of previously reported values.