Bioassay guided fractionation of an ethanolic extract of Polygonum amplexicaule D. Don led to the isolation of amplexicine, a new flavan-3-ol (1), along with khellactone (2). The structure of the isolates was established by UV, IR, HRESI/MS and NMR, including 1D and 2D experiments. Compound 1 exhibited considerable antioxidant activity in a 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging assay.