Proanthocyanidins　from　the　rhizomes　of　Selliguea　feei　(PSFs)　were　solvent-extracted　and　fractionated　by　Sephadex　LH-20　column　chromatography　to　give　a　2.42%　isolated　yield　(dry　matter　basis).　1H-NMR　spectroscopy　revealed　the　mean　degree　of　polymerization　(mDP)　to　be　2.6.　13C-NMR　analysis　showed　typical　signals　for　afzelechin/epiafzelechin　units.　Clear　peaks　at　76　ppm　and　84　ppm　indicated　that　both　stereoisomers　(afzelechin/　epiafzelechin)　are　present.　In　agreement　with　the　NMR　spectra,　the　ESI-MS　spectrum　indicated　that　PSFs　are　mainly　monomers　to　trimers　consisting　of　afzelechin/epiafzelechin　units　with　A-type　and　B-type　interflavanyl　linkages.　A　trimer　was　purified　and　identified　as　demethylated　selligueain　B.　Thiolysis　confirmed　the　structure　and　the　thiolytic　products,　methyl　2-[(2R,　3R,　4S)-3,5,7-trihydroxy-2-(4-hydroxyphenyl)chroman-4-yl]acetate　(1)　and　4β-(carboxymethyl)sulphanylepiafzelechin-(2β→O→7,　4β→8)-epiafzelechin　methyl　ester　(2),　were　purified　and　characterized.　Selligueain　A,　demethylated　selligueain　B,　compounds　1　and　2　possess　high　antioxidant　capacity　at　1.18　×　104,　1.16　×　10　4,　0.95　×　104　and　1.29　×　104　μmol　TE/g,　respectively.　©　2013　by　the　authors.