Polysaccharides are important active ingredients of living organisms. In this study, two new polysaccharides,Tricholoma sinoportentosumpolysaccharide (TS-P) andTermitomyces albuminosus(TA-P), were extracted and purified using anion exchange column chromatography. The structure of each polysaccharide was identified by HPGPC, FT-IR, HPLC, GC-MS and NMR, and the biological activities were also investigated. The results of the structure identification showed that TS-P was composed of arabinose, mannose, glucose and galactose at a ratio of 1:1:3:2 and its main chain was composed of (1→4)-Arap residues, (1→4,6)-D-Manp residues and two (1→6)-Galp residues. The TA-P was composed of arabinose, glucose and galactose at a ratio of 2:4:8. Its main chain was composed of two (1→4)-β-L-Arap residues, one (1→4)-Glcp residues, three (1→2,6)-Galp residues and five (1→6)-Galp residues. The immunoassay showed that TS-P and TA-P could significantly promote the proliferation of T cells, B cells and RAW264.7 cells. The cell cycle results showed that for B cells and macrophages, TS-P and TA-P mainly affected the G0/G1 phases of the cell cycle; for T cells, TS-P affected G2/M phase, while TA-P mainly affected the G0/G1 phases. TS-P could significantly promote B cells to secrete IgA, IgG and IgD (p< 0.01), while TA-P could significantly promote the secretion of IgA and IgG (p< 0.01). The chemical structure and biological activity of TS-P and TA-P were first studied and compared to lay a theoretical foundation for the application of fungal polysaccharide.