Complexes of chitosan with Mn(Ⅱ) were prepared by adding Mn(OAc)2·4H2O to Chitosan solution. IR, elemental analysis and TG analysis were used to character the complex. The results showed that there were coordinate bands formed. H2O2 was used to degrade chitosan-Mn(Ⅱ) complex, and the molecular distribution of degraded products were investigated after eliminating Mn(Ⅱ) ions using the cation exchange resin column. The result suggested that the Chitosan could be degraded rapidly, the degradation started from higher molecular weight range, the molecular weight distribution of oligosaccharides was much more narrower than that of degradated products from common methods such as hydrolysis, acidic and oxidizing methods. The index of molecular weight distribution was changed with the average degradability. When exceeding 10 oligosaccharides, the smaller of the DP, the smaller of the index.