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<i>Acanthopanax sessiliflorus</i> (Rupr. & Maxim.) Seem. (<i>Araliaceae</i>) is one of the most abundant species of genus <i>Acanthopanax</i>. The fruits of <i>A. sessiliflorus</i> are used in traditional medical protocols as an analgesic, tonic, antidiabetic, antihypertensive, anti-inflammatory, antitumor, and immune-stimulating agent. In this work, we carried out a comprehensive investigation into the anthocyanin components in the fruits of <i>A. sessiliflorus</i>. The anthocyanin content in the fresh fruits of <i>A. sessiliflorus</i> was determined by high performance liquid chromatography-diode array detection (HPLC/DAD), and the anthocyanin component was isolated from these using high-speed counter-current chromatography (HSCCC) and elucidated by electro-spray ionization-mass spectrometry (ESI/MS), ¹H- and ¹³C-NMR. Its antioxidant activity was evaluated by ferric-reducing antioxidant power (FRAP) and 2,2-diphenyl-1-picrylhydrazyl (DPPH). We found that <i>A. sessiliflorus</i> contained a gross anthocyanin content of 121.35 mg/100 g. HSCCC was successfully used for separation and purification of the primary anthocyanin component, cyanidin 3-xylosyl-galactoside. The antioxidant and radical scavenging tests indicated that cyanidin 3-xylosyl-galactoside is a potent antioxidant.