A new neutral polysaccharide, named AGP, was extracted from glycyrrhiza residue by 5% NaOH alkaline solution and purified by DEAE-cellulose and Sephadex G-150. A single and symmetrical peak was shown by HPLC, indicating that AGP is a homogeneous polysaccharide with a molecular weight of 2.89 × 103 KDa. The specific rotation of AGP was detected by a polarimeter and it was +45°. Monosaccharide composition analysis indicated that AGP was consisted of l-rhamnose: l-arabinose: d-xylose: d-mannose: d-glucose and d-galactose with a molar ratio of 1:2.33:2.85:0.69:3.05:1.54. The structure of AGP was analyzed by GC–MS, periodate oxidation, Smith degradation, FT-IR, methylation and NMR, which indicated that the AGP was composed of → 6)-β-d-Glcp-( → backbone and the →4)-α-d-Xylp-(1→, →5)-α-l-Araf-(1→, →3)-α-l-Rhap-(1→, →6)-α-d-Galp-(1→, →3,6)-α-Manp-(1→ and →1)-β-d-Glcp as branches. The results of Congo red experiment and circular dichroism (CD) showed that there was triple helix conformation in AGP. The micro-structure of AGP were detected by scanning electron microscopy (SEM), which concluded that the shape of AGP was a “thin slice” and its structure is not regular. The crystal configuration was identified by X-ray diffraction (XRD), showing that there is no crystal structure. Furthermore, the AGP exhibited certain inhibition activity on α-glucosidase.