In this study, the ultrasound-assisted enzyme extraction method was used to extract polysaccharide (StPP) from Shatian pomelo peel, which was then separated and purified by DEAE-52 and Sephadex G-100. Finally, two different polysaccharide fractions were obtained and named StPP-2 and StPP-3. In addition, the structures of the two fractions were analyzed by NMR and IR. The results showed that StPP-2 primarily contains →4)-β-d-Glcp (1→ glycosidic bonds, while STPP-3 contains mainly α-d-GalA glycosidic bonds. StPP-3 has a triple helix structure, but StPP-2 does not. The in-depth study of StPP is of great practical significance in exploring the multifaceted utility of Shatian pomelo peel.