ABSTRACT:Black ginseng (BG), a novel manufactured ginseng product, is gaining market attention due to its high polarity and similar structure constituents. In this work, the primary constituents of Panax quinquefolium L. BG, including ginsenosides and derivatives, were separated using high‐speed counter‐current chromatography in conjunction with evaporative light scattering detection by recycling and consecutive mode, as well as the elution‐extrusion method for continuous sample loading. Sample loading and mobile phase ratios were among the optimized primary separation parameters. Nine compounds, including ginsenoside Rg6 (1), 22(E)‐ginsenoside F4 (2), ginsenoside Rk3 (3), ginsenoside Rh4 (4), ginsenoside Rg3 (5), 20(R)‐ginsenoside Rg3 (6), (3R,9R,10R)‐panaxytriol (7), ginsenoside Rk1 (8), and ginsenoside Rg5 (9), were ultimately effectively isolated. Mass spectrometry and nuclear magnetic resonance spectrometry were used to investigate the structures. Based on our research, the developed process was a successful way to separate the primary ingredients from BG. Purification of additional comparable high‐polarity chemicals from complicated natural products might be accomplished using the stated methodology.