The dewaterability of excess sludge significantly improved upon pretreatment with Fenton's reagent in this study. After 0.9 g/L of Fe2+ and 5.0 g/L of H2O2 were added to the sludge, and reacted for 2 h at pH = 4, the specific resistance to filtration (SRF) of the excess sludge decreased from an initial value of 29.74 × 1012 m/kg to 6.49 × 1012 m/kg. The factors that affected this improvement in sludge dewaterability as evaluated by SRF reduction showed the following order: H2O2 > pH > Fe2+ > reaction time. Furthermore, the hydrolysis performance of the sludge under the optimal reaction conditions was investigated. The results indicated that the concentration of soluble chemical oxygen demand in the supernatant increased almost 14 times compared to raw sludge, and the contents of soluble protein and soluble polysaccharide were more than 8 and 17 times higher, respectively, than for the untreated situation. However, the amounts of ammonia nitrogen (NH4+-N) and phosphate (PO43−-P) released from the sludge showed different trends: NH4+-N increased by 200%, while PO43−-P decreased by 82%. The production of volatile fatty acids (VFAs) from the treated sludge showed that total VFAs increased by 66%, and iso-butylacetic acid was the dominant product among the total VFAs.