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A polysaccharide (LPR) was separated from the roots of Lilium davidii var. unicolor Cotton with hot water extraction, ethanol precipitation, and purification by anion-exchange and gel-permeation chromatography. LPR was characterized. The weight-average molecular weight (M W) of LPR was 5.12 × 104 g/moL. Glucose and mannose comprised LPR with a molar ratio of 2.9:3.3. IR, NMR and methylation analysis showed that LPR was a natural O -acetyl glucomannan, the backbone mainly contained β-(1 → 4)-linked d -glucopyranosyl and β-(1 → 4)-linked D-mannopyanosyl, and the branches probably linked at O-2 and/or O-3 of the mannosyl and glucosyl residues. The acetyl groups mainly attached at O-2 or O-3 of mannosyl residues. X-ray diffractometric (XRD) analysis and scanning electron microscopy (SEM) analysis revealed that LPR was a semi-crystalline substance with porous lamellar structure. Bioassays in vitro indicated that LPR had distinct scavenging activities on hydroxyl radical and DPPH radical. These findings provided a reference for functional underutilization roots of L. davidii as natural antioxidant in food and pharmaceutical industry. Unlabelled Image • First report structure and bioactivities of polysaccharide (LPR) purified from the roots of L. davidii. • LPR was a glucomannan with O -acetyl group attached. • LPR was a semi-crystalline substance with porous lamellar structure. • LPR to scavenge hydroxyl radical stronger than that of Vc (especially the concentration < 0.3 mg/mL). [ABSTRACT FROM AUTHOR]