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The alpha-D-glucans are worldwide acknowledged as powerful immune system stimulants found in several sources; however, the fungal-derived sources appear to respond with higher activity. The present study has investigated polysaccharide production in Moniliophthora perniciosa. The dry biomass was subjected to thermal treatment in alkaline solution after fermentation. The biopolymers dissolved in this solution were precipitated after three volumes of absolute ethanol were added to the supernatant. The pure polysaccharide MPS1 was obtained through molecular exclusion chromatography using the Sephacryl S-200 column. The HPLC-RI analysis showed that MPS1 was a glucose homopolysaccharide. Nuclear magnetic resonance (NMR) spectra indicated the α-form as the anomeric carbon configuration in glucose residue. The structure of the polysaccharide was further confirmed as (1→4)-α-D-glucan through the chemical shift of C4. The molecular weight of MPS1 was 31.0 kDa.