This paper investigates the behavior of different sludges from several treatment plants at full and pilot scale configured as Conventional Activated Sludge (CAS) and Membrane Bio Reactor (MBR) plants treating different kinds of wastewaters. The sludges collected were subjected to complete analytical and technological characterization in order to correlate the rheological properties that affect the dewatering behavior to the sludge chemical physical properties. In detail the EPS from the samples collected is extracted and characterized in terms of carbohydrates, proteins, uronic acids and humic acids content. Moreover, once characterized, the sludges were subjected to AD in order to assess their bio-methanation potential and hence their biological stability. The final aim was to find correlations between the WWTP operational parameters (i.e. HRT, SRT, volumetric load coefficient, aeration) that finally affect its chemical composition (i.e. BMP, EPS composition) and the physical behavior of the sludge