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In this study, a pectin polysaccharide, AER-A3 (Mw 1.12 × 105 g/mol), was isolated and purified from the root bark of Aralia elata by ion exchange and gel-filtration chromatography. Its planar structure was investigated in combination with UPLC-ESI-MS, FT-IR, HILIC-ESI--MS/MS, GC-MS and NMR techniques. The main chain of AER-A3 was unambiguously determined to be smooth region and hairy region with a chain length ratio of 11 characterized by occurrence of (1 → 2)-α-Rhap, (1 → 2,3)-α-Rhap, (1 → 2,4)-α-Rhap, (1 → 2,3,4)-α-Rhap, and (1 → 4)-α-GalpA, whereas the