A preparative high-speed counter-current chromatography (HSCCC) method for separation and purification of phenolic acids from the Chinese medicinal herb Smilax china was successfully established by using n-hexane-ethyl acetate-methanol-water (1:21:2, v/v/v/v) as the two-phase solvent system. The experiment yielded 26.7 mg of gallic acid, 16.5 mg of protocatechuic acid, 21.8 mg of caffeic acid, 31.3 mg of gentisic acid, and 24.1 mg of trans-o-coumaric acid from 250 mg of crude extract in one-step separation, of each at over 98% purity as determined by high-performance liquid chromatography (HPLC). The structures of these compounds were identified by electron spray ionization mass spectroscopy (ESI-MS), H-1 and C-13 nuclear magnetic resonance (NMR). (c) 2008 Elsevier B.V. All rights reserved.