SummaryThe simultaneous quantitation of acids and sugars as their trimethyl silyl (TMS) derivatives has been extended in order to identify and quantitate the simple acid and sugar constituents in the hydrolyzates of various immunostimulant, water-soluble polysaccharides obtained from various Basidiomycetes, such as Armillariella mellea, Auricularia auricula-judae, Coriolus versicolor, Flammulina velutipes, Fomes fomentarius, Ganoderma applanatum, Ganoderma lucidum, Pleurotus ostreatus, Schizophyllum commune, Trametes hirsuta. Optimum hydrolysis conditions, performed with 2 M trifluoroacetic acid (TFAA) for five hrs, proved the presence of several sugars and acids with maximum recovery. (i) The total sugar/sugar alcohol content of polysaccharides varied between 20-and 65 % and consisted of arabitol (0.01-10.2 %), arabinose (0.09-1.3 %), ribose (0.2-1.8 %), fucose (0.3-1.2 %), mannitol (0.01-5.3 %), sorbitol (0.01-0.05 %), galactitol (0.04 %), fructose (0.08-0.8 %), galactose (0.9-29 %), glucose (10-53 %), uronic acids (0.14-3.7 %), sucrose (0.03-2 %), trehalose (0.2-1%), cellobiose 0.01-0.6 %), maltose 0.2-1.9 %), other disaccharides (0.2-8 %). (ii) The total of acids varied from 1.5 to 30 % including o-phosphoric (1.3-19 %), malic (0.08--4.7 %), citric (0.08-4.7 %), isocitric; (3 %) and C16-C18 fatty acids (1-6 %).