In this work, the effect of Fenton's reagent on the degradation of residual Kraft black liquor was investigated. The effect of Fenton's reagent on the black liquor degradation was dependent on the concentration of H2O2. At low concentrations (5 and 15 mM) of H2O2, Fenton's reagent caused the degradation of phenolic groups (6.8 and 44.8%, respectively), the reduction of reaction medium pH (18.2%), and the polymerization of black liquor lignin. At a high concentration (60 mM) of H2O2, Fenton's reagent induced an extensive degradation of lignin (95-100%) and discoloration of the black liquor. In the presence of traces of iron, the addition of H2O2 alone induced mainly lignin fragmentation. In conclusion, Fenton's reagent and H2O2 alone can degrade residual Kraft black liquor under acidic conditions at room temperature.