Introduction: Polygonatum cyrtonema Hua. (PC) is a traditional Chinese herb with a history of use in both food and medicine. For clinical use, processed PC pieces are most commonly used, while present research has focused on crude PC polysaccharides (PCPs).Methods: In this study, a new polysaccharide, PCP-F1, with a molecular weight of 37.46 kDa, was separated from four-time processed PCPs by column chromatography and evaluated by antioxidant activity. It was composed of glucose, mannose, galactose, rhamnose, and galacturonic acid with a molar ratio of 3.5: 2.5: 1.3: 1.8: 0.8.Results and Discussion: The methylation analysis and two-dimensional NMR measurement revealed that the configuration of PCP-F1 contained nine residues in the primary structural unit by the chain of →3)-α-D-Glcp, →2)-α-D-Glcp (6→, →1)-ꞵ-D-Glcp (2→, →2)-α-D-GalAp (3,4→, →1) -ꞵ-D-Manp (3→, →2)-α-D-Glcp (3→, branched for →3)-α-D-Glcp, →2)-ꞵ-D-Galp (4→, →1)-ꞵ-D-Glcp (2→, →2,4)-α-D-Manp (6→, →3)-α-L-Rhap (4→. Radical scavenging assays indicated that PCP-F1 could scavenge radicals with a high scavenging rate, suggesting PCP-F1 possesses good antioxidant activity. The study confirms the importance of processed PC and offers the potential for exploiting it as a functional food.