Objective: To isolate and purify the crude polysaccharide from Polygonatum odoratum and then to identify the chemical structure. Method: A polysaccharide-rich extract was obtained by hot water extraction from Polygonatum odoratum and purified by grading ethanol precipitation and collect the precipitate at 80% volume fraction of ethanol, were sequentially purified by DEAE-cellulose chromatography and Sephadex G-100 molecular sieve chromatography and an acidic polysaccharide fraction named POAP80 was obtained. The purity of POAP80 was identified by UV absorption spectrum, IR spectrum and paper chromatogram. The monosaccharide compositions of POAP80 were analyzed by infrared spectroscopy and PMP pre-column derivatization high performance liquid chromatography. Result: An acidic polysaccharide was isolated and purified from Polygonatum odoratum and it was mainly composed of mannose, glucose, galacturonic acid and galactose at a molar ratio of 0.93: 2.65: 29.38: 3.47. Conclusion: POAP80 was found in the Polygonatum odoratum for a novel component. The structure information POAP80 was obtained through the above-mentioned methods, which provides the basis for the further study of the constitution and function of POAP80.