The physicochemical properties of Phellinus baumii polysaccharides extracted from the fruiting bodies by different grinding methods were studied in this paper. Compared with ordinary grinding methods, superfine grinding technology exerts significantly higher yields of crude polysaccharides, polysaccharide contents and β-Glucan contents of six samples. HPSEC-MALLS- RI analysis shows the molecular weight distribution of P.baummii crude polysaccharides, which indicates superfine grinding technique generates higher molecular weight fractions and larger polydispersities. The 6 kinds of crude polysaccharides have obvious effects on NO generation of RAW264.7 cells, which indicated that crude polysaccharides from P.baumii may have some immune-enhancing effects. Meanwhile, CW30 and FP30 show the best immune enhancing effects. However, CW50 and CW70 exert weaker immune-enhancing effects compared with FP50 and FP70.