Polysaccharides were extracted by hot water and alkali in sequence from Dolichos lablab L. hull, and further purified by ion-exchange and gel columns. Hot water extracted D. lablab hull polysaccharide (DLHP) was rich in glucuronoxylan and pectin, and alkali extracted polysaccharide (DLHAP) mostly embraced glucuronoxylan. The structures of purified glucuronoxylans from DLHP and DLHAP were mainly analyzed by HPAEC-PAD, methylation combined with GC-MS, NMR and SEC-MALLS. DLHP-1 was identified as acetylated glucuronoxylan containing →4)-β-Xylp-(1→ backbone with substitution at O-2 site by α-GlcpA/4-O-methyl-α-GlcpA. The molar ratio of β-Xylp to α-GlcpA was 6.9:1, and acetylation was mainly at O-3 site of β-Xylp with acetylation degree of 21.5%. DLHP-1 and DLHP-2 had similar physicochemical properties, except for molecular weight (Mw). DLHAP-1 was the non-methylated glucuronoxylan almost without acetylation, and it had the molar ratio of β-Xylp to α-GlcpA of 5.6:1. Besides, DLHP-1 (Mw of 20.0 × 103 g mol-1) adopted semi-flexible chain, while DLHAP-1 (Mw of 15.4 × 103 g mol-1) showed flexible chain. These results provided a structural basis for study on polysaccharides from D. lablab hull, which was benefit for understanding biological activities and developing functional food or pharmaceuticals of D. lablab.