Stilbenoids are the main components of leaves and stems of Pholidota chinensis. In the present investigation, high-speed counter-current chromatography was used for the separation and purification of two classes of stilbenoids, namely, bibenzyls and 9,10-dihydrophenanthrenes, on a preparative scale from whole plants of P. chinensis with different solvent systems after silica gel column chromatography fractionation. n-Hexane/ethyl acetate/methanol/water (1.2:1:1:0.8, v/v/v/v) was selected as the optimum solvent system to purify 1-(3,4,5-trimethoxyphenyl)-1',2'-ethanediol (1), coelonin (2), 3,4'-dihydroxy-5,5'-dimethoxybibenzyl (3), and 2,​7-​dihydroxy-​3,​4,​6-​trimethoxy-​9,​10-​dihydrophenanthrene (4). While 2,7-dihydroxy-3,4,6-trimethoxy-​9,​10-​dihydrophenanthrene (5), batatasin III (6), orchinol (7), and 3'-O-methylbatatasin III (8) were purified by n-hexane/ethyl acetate/methanol/water (1.6:0.8:1.2:0.4, v/v/v/v). After the high-speed counter-current chromatography isolation procedure, the purity of all compounds was over 94% assayed by ultra high performance liquid chromatography. The chemical structure identification of all compounds was carried out by mass spectrometry and (1)H and (13)C NMR spectroscopy. To the best of our knowledge, the current investigation is the first study for the separation and purification of bibenzyls and 9,10-dihydrophenanthrenes by high-speed counter-current chromatography from natural resources.