Extracellular polymeric substances (EPS) in sewage sludge are highly hydrophilic, and the destruction of EPS structure is very essential for the high-performance dewatering process. In this study, the peracetic acid lysis and chemical re-flocculation was used to achieve the volume reduction and dewaterability improvement of waste activated sludge. Moreover, dynamic variations of the floc morphology and EPS properties of sludge were also investigated. The results indicated that PAA treatment had very limited effect on sludge filterability, while filtration drying performance was effectively improved. PAA could effectively solubilize the sludge particle and destroy the protein-like substances, resulting in an efficient releasing of bound water. Sludge dewatering was enhanced under a low pH level after PAA oxiution, ascribing to the higher oxiutive ability of PAA under acid conditions. No integral sludge floc could be observed after PAA treatment at high dosages. Floc reformed after the additive of PAC and ferric chloride, meanwhile both filterability and dewaterability were improved. Furthermore, PAC performed better in improving sludge dewatering performance than ferric chloride due to its high adsorption and bridging abilities.