Purple mangosteen scarfskin polysaccharide has many important physiological functions, but its preparation method, structure, and function need further exploration. A polysaccharide was obtained from mangosteen scarfskin by ultrasonic-assisted extraction and purified. On this basis, its structure and physicochemical properties were investigated. The Congo red experiment was used to determine whether it has a triple helix conformation. The structure of purple mangosteen scarfskin polysaccharide was further analyzed by infrared spectroscopy and nuclear magnetic analysis. The antioxidant activities of the above three polysaccharides were studied by related experiments. It was found that the monosaccharide composition of purple mangosteen scarfskin polysaccharide mainly contained a large amount of arabinose, a small amount of rhamnoose and a very small amount of galacturonic acid, and its core main chain was composed of 1,4-α-arabinose. It did not have this spatial configuration. After the acetylation of purple mangosteen scarfskin polysaccharide, the acetylated derivative with a degree of substitution of 0.33 was obtained. It was found that they had certain scavenging and inhibiting effects on hydroxyl radicals and lipid peroxidation, and their activities were related to the concentration of polysaccharides. Meanwhile, the antioxidant activity of the polysaccharide was significantly enhanced after the modified treatment of acetylation, which indicated that chemical modification could effectively improve some activities of polysaccharide. The above studies provided some reference value for the further research and development of purple mangosteen scarfskin polysaccharide.