The polysaccharide PMEP-1 was isolated from Morchella esculenta (L.) Pers. through hot-water extraction and subjected to Sevag deprotein, dialysis, ethanol precipitation, DEAE-52 cellulose ion-exchange column chromatographic analysis and Sephadex G-100 column chromatographic analysis. This polysaccharide was found to be highly homogeneous with a relative molecular mass of 43600 and a specific rotation of +257.0 (C = 0.001, H2O) and the yield reached 1.58%. The chemical structure of PMEP-1 was analyzed by chemical methods (including partial hydrolysis with acid, methylation reaction, periodate oxidation, and Smith degradation) and instrument analysis methods (using IR, GC-MS, 1H-NMR, and 13C-NMR). The polysaccharide PMEP-1 was found to be composed of Ara, Man, Glc and Gal with a molar ratio of 1: 2.37: 4.79: 3.09 and be a complex heteropolysaccharide with highly ramified structure, whose main chain was formed by a mixing linkage of α-1,4-glucose, α-1, 6-galactose, α-1,2-mannose and α-1,5-arabose and whose side chains were attached at α-1,2,6-mannose, α-1,4,6-glucose and α-1,2,6-galactose.