In order to obtain the chitosan oligomers, chitosan was irradiated in the solid state with and without H2O2 as a radiation degradation sensitizer, respectively. At room temperature, the viscosity average-molecular weight (Mη) of chitosan was decreased from 1.6 × 106 to 2.2 × 105 at an absorbed dose of 72 kGy without H2O2, and decreased to 2.7 × 104 at 2 kGy in the presence of an appropriate H2O2 content. In addition, the radiation degradation rate of chitosan containing 38.2wt%H2O2 is 59 times higher than that in the solid state without H2O2. FT-IR analysis suggests that there is no obvious change in the chemical structure of irradiated chitosan with and without H2O2 at a dose below 20 kGy, compared with unirradiated chitosan. On the other hand, the degree of deacetylation (DD) of irradiated chitosan in the studied dose range changed slightly, while DD of irradiated chitosan with H2O2 increased significantly. The XRD pattern indicates that the irradiated chitosan with H2O2 has more perfect crystalline structure than unirradiated chitosan. Therefore, it could be expected that irradiation of chitosan using H2O2 as a sensitizer would be a very effective method to prepare low molecular weight chitosan,because of its feasibility and benignancy to environment.