pH-zone-refining counter-current chromatography was successfully applied to the separation of cichoric acid from Echinacea Purpurea (L.) Moench. A 3.0 g quantity of sample was separated using the following two-phase solvent system: MtBE-CH3CN-water (4:1:5, v/v), 10 mM trifluoroacetic acid in organic stationary phase and 10 mM ammonia in aqueous mobile phase. The obtained fractions were analyzed by high-performance liquid chromatography and negative ion electrospray ionization mass spectrometry. Double separations were performed with the same solvent system yielding 563 mg cichoric acid at 95.6% purity.