Abstract This study focuses on improving the efficiency of the microwave (MW) pretreatment of waste activated sludge (WAS) through deflocculation mediated by sodium tripolyphosphate (STPP), a cationic binding agent. Deflocculated sludge was subjected to MW pretreatment to assess its impact on biomass disintegration. At the optimised energy for MW pretreatment (14,000 kJ/kg TS), the chemical oxygen demand (COD) solubilisation was 28% and 21% and the reduction in suspended solids (SS) was 38% and 26%, respectively, for deflocculated (treated with a cationic binding agent followed by microwaves) and flocculated (treated by microwaves alone) sludge samples. The formation of volatile fatty acids in the deflocculated sludge medium (840 mg/L) was comparatively higher than that in the flocculated sludge (420 mg/L) and the control (62 mg/L). This study indicates that deflocculated sludge is more amenable to hydrolysis. The results of a test of biochemical methane potential also confirmed the greater amenability of deflocculated sludge for anaerobic degradation.