Two polysaccharides were isolated from submergedly cultured mycelium of the basidiomycete Ganoderma lucidum by extraction with alkali followed by fractionation with Fehling reagent. The polysaccharides were shown to be a linear (1-->3)-alpha-D-glucan and a highly branched xylomannan containing a backbone built up of (1-->3)-linked alpha-D-mannopyranose residues, the majority of which are substituted at O-4 by single beta-D-xylopyranose residues or by disaccharide fragments beta-D-Manp-(1-->3)-beta-D-Xylp-(1-->. Polysaccharide structures were elucidated by NMR spectroscopy in combination with methylation analysis and periodate oxidation. An interesting feature of the xylomannan is the simultaneous presence of alpha-D-mannopyranose and beta-D-mannopyranose residues, the first forming the backbone, and the second being the non-reducing terminal units of disaccharide side chains.