•Sludge dewaterability was improved by Fe(II)-PMS with high CST and SRF reduction.•Optimal conditions were identified: PMS 0.9mmol/gVSS, Fe(II) 0.81mmol/gVSS, pH 6.8.•The protein in EPS conducted a detrimental influence on sludge dewaterability.•The release of EPS-bound water induced the enhanced sludge dewatering. The effect of Fe(II)-activated peroxymonosulfate (Fe(II)-PMS) oxidation on the waste activated sludge (WAS) dewatering and its mechanisms were investigated in this study. The capillary suction time (CST), specific resistance to filterability (SRF) of sludge and water content (WC) of dewatered sludge cake were chosen as the main parameters to evaluate the sludge dewaterability. Experimental results showed that Fe(II)-PMS effectively disintegrated sludge and improved sludge dewaterability. High CST and SRF reduction (90% and 97%) was achieved at the optimal conditions of PMS (HSO5-) 0.9mmol/gVSS, Fe(II) 0.81mmol/gVSS, and pH 6.8. Extracellular polymeric substances (EPS) and three-dimensional excitation–emission matrix (3D-EEM) fluorescence spectroscopy before and after Fe(II)-PMS oxidation were determined to explain the enhanced dewatering mechanism. The release of EPS-bound water induced by the destruction of EPS was the primary reason for the improvement of sludge dewaterability during Fe(II)-PMS oxidation.