Anoectochilus roxburghii (AR) has been used in food, medicine and ornamental industries for a long time. Anion exchange resin was proposed to purify the sub-fraction of water-extracted AR polysaccharide (ARPP-70), and a homogeneous polysaccharide ARPP-70a was obtained. The structural features of ARPP-70a were characterized using gas chromatography–mass spectrometry (GC–MS), nuclear magnetic resonance (NMR) spectroscopy, and high performance size exclusion chromatograph coupled with multi-angle laser light scattering (HPSEC-MALLS). The relative weight average molecular weight for ARPP-70a was determined to be 14.8 kDa, and the molar ratio of glucose to galactose was 1.0:3.2. The structure of ARPP-70a was elucidated to be glucogalactan, with backbone comprising β-1,4-linked Galp and some α-1,4-linked Glcp. The conformation characteristics of ARPP-70a were supposed to exist as a random coil chain in 0.1 M NaNO3 solution. Moreover, in vitro antioxidant activity assays revealed ARPP-70a exhibited appreciable antioxidant potential. To the best of our knowledge, this is the first study to obtain this type of glucogalactan, and provide systematic information on its structural and conformational properties. This study improved the understanding of the physicochemical characteristics of AR polysaccharide, which is beneficial for its further application in food and medicinal industry.
