Four polysaccharide fractions (P‐1: 71.40%, P‐2: 1.95%, P‐3: 1.14%, P‐4: 1.64%) were isolated from crude Polygonatum sibiricum polysaccharide (PSP), processed by water extraction, ethanol precipitation, and further separated with diethylaminoethyl cellulose‐52 anion‐exchange chromatography. Their molecular weights and monosaccharide compositions were characterized by high performance gel chromatography with evaporative light scattering detector and ultraviolet–visible detector. The antioxidant activity of four polysaccharides fractions were assessed by the electron transfer menchanism (DPPH, ferric reducing power, and ABST assays) and chelation of transition metals (Fe2+ and Cu2+ chelation ability). The highest content fraction P‐1 exhibited the lowest antioxidant activity, and the ranking of antioxidant capacity was P‐4 > P‐3 > P‐2 > PSP > P‐1. After processed by microwave‐assisted degradation, the molecular weight of P‐1 was decreased from 2.99 × 105 to 2.33 × 103 Da, while the antioxidant activity of degraded P‐1 was about eightfold higher than natural P‐1. These results indicated that the proposed microwave‐assisted degradation approach was an efficacious methodology to improve their bioactivity by lower the molecular weight of polysaccharides. Practical Application This study provided an environmentally friendly, convenient and efficient microwave‐assisted degradation technology to process the neutral polysaccharides from Polygonatum sibiricum. The results could be used for the development and utilization of various plant polysaccharides as a kind of food supplement in our daily life.