The management of wastewater sludge, now often referred to as biosolids, accounts for a major portion of the cost of the wastewater treatment process and represents significant technical challenges. In many wastewater treatment facilities, the bottleneck of the sludge handling system is the dewatering operation. Advanced sludge treatment (AST) processes have been developed in order to improve sludge dewatering and to facilitate handling and ultimate disposal. The authors have extensively reported lab-scale, semi-pilot and pilot investigations on either thermal and thermochemical processes, or chemical oxidation using hydrogen peroxide. To understand the action of these advanced sludge technologies, the essential role played by extracellular polymeric substances (EPS) needs to be understood. EPS form a highly hydrated biofilm matrix, in which the micro-organisms are embedded. Hence they are of considerable importance in the removal of pollutants from wastewater, in bioflocculation, in settling and in dewatering of activated sludge. The present paper reviews the characteristics of EPS and the influence of thermochemical and oxidation mechanisms on degradation and flocculation of EPS. Experimental investigations on waste activated sludge are conducted by the authors to evaluate the various literature findings. From the experiments, it is concluded that AST methods enhance cake dewaterability in two ways: (i) they degrade EPS proteins and polysaccharides reducing the EPS water retention properties; and (ii) they promote flocculation which reduces the amount of fine flocs.