High-performance countercurrent chromatography (HPCCC) with electrospray light-scattering detection was applied for the first time to isolate a spirostanol and a novel furostanol saponin from Liriope platyphylla . Due to the large differences in K D values between the two compounds, a two-step HPCCC method was applied in this study. The primary HPCCC employed methylene chloride/methanol/isopropanol/water (9:6:1:4 v/v, 4 mL/min, normal-phase mode) conditions to yield a spirostanol saponin ( 1 ). After the primary HPCCC run, the solute retained in the stationary phase (SP extract) in HPCCC column was recovered and subjected to the second HPCCC on the n -hexane/ n -butanol/water system (1:9:10 v/v, 5 mL/min, reversed-phase mode) to yield a novel furostanol saponin ( 2 ). The isolated spirostanol saponin was determined to be 25( S )-ruscogenin 1- O -β- d -glucopyranosyl (1→2)-[β- d -xylopyranosyl (1→3)]-β- d -fucopyranoside (spicatoside A), and the novel furostanol saponin was elucidated to be 26- O -β- d -glucopyranosyl-25( S )-furost-5(6)-ene-1β-3β-22α-26-tetraol-1- O -β- d -glucopyranosyl (1→2)-[β- d -xylopyranosyl-(1→3)]-β- d -fucopyranoside (spicatoside D).