The order Aphyllophorales is an important group of the Basidiomycota. Many species are effcient in decomposing plant materials because they can digest cellulose and/or lignin wich constitute the plant cell wall. The defatted powdered fruiting body from Ganoderma multiplicatum was submitted to hot water and 2%, 10%, 20% and 30% aq. KOH extractions. The aqueous extract was treated with excess EtOH, such the alkali extract were treated with HOAc (~ pH 5.0). The resulting extracts were submitted to freeze-thawing, Fehling solution precipitation, ultrafiltration and/or dialyses membrane filtration with differences cut-offs. The fractions 10ESFW and 10RSFW, obtained after ultrafiltration through a M_r 10 kDa cutt-off membrane from aqueous extraction, gave a homogeneous profile (HPSEC) and glucose was its main component. The ¹³C NMR spectrum contained C-1 signals at d 102.7 and 102.3 suggesting a b-configuration. Other C-1 signals of low intensity at d 100.3 and 97.7 showed a a-configurations. These results suggest a glucan containing both a- and b- configurations. The fractions 10ESFK2 and 10RSFK2 soluble in Fehling solution and filtrated through a M_r 10 kDa cutt-off membrane from the extraction with 2% aq. KOH was homogeneous (HPSEC) and contained mainly, glucose. The ¹³C NMR, DEPT spectrum and methylation analysis suggest a branched b-glucan containing (1®3) and (1®6) linkages, beside (1®4)-linked units. A xylomannan, containing a main chain of (1®4)-linked a-D-Manp substituted in the position O-3 with non-reducing end-groups of b-Xylp, was purified from the 10% aq. KOH extract. These results were confirmed by ¹³C NMR and methylation analysis. A linear (1®3)-linked b-glucan, namely laminaran, was isolated from the 20% aq. extract. A similar structure was obtained from the 30% aq. KOH extraction. The polymer consist of a b-glucan with a main chain of (1®3)-linked units substituted in the position O-6 with (1®4) linked b-Glcp chains. These data were confirmed by methylation analysis, Smith degradation and ¹³C NMR.