A heteropolysaccharide was isolated from the fruiting bodies of Amanita caesarea using a diethylaminoethyl-cellulose column, Sephacryl S‑300 gel column and Sephadex G‑200 column. The Amanita caesarea polysaccharide was predominantly composed of α-D-glucose and α-D-lyxose at a ratio of 2:1, and it had a molecular weight of 19,329 Da. The structural features of the Amanita caesarea polysaccharide were investigated by a combination of total hydrolysis, methylation analysis, gas chromatography-mass spectrometry, and infrared spectra and nuclear magnetic resonance spectroscopy. The results showed that Amanita caesarea polysaccharide (termed AC‑1) had a backbone of 1,4‑linked α‑D‑glucose and 1,3,6‑linked α‑D‑glucose, with branches of one 1‑linked α‑D‑lyxose residue. The antioxidant activity of AC‑1 was evaluated by two biochemical methods, 2,2-azino-bis diammonium (ABTS+) radical scavenging activity and 1,1-diphenyl-2-picrylhydrazyl (DPPH-) radical scavenging activity. The uncontrolled production of free radicals is involved in various diseases, including cancer, atherosclerosis and degenerative aging processes. The results indicated that the Amanita caesarea polysaccharide exhibits strong antioxidant activity, thus, it may be a useful natural product antioxidant.