The potential benefits of Fe(II)-activated persulfate (S(2)O(8)(2-)) oxidation under mild temperature in enhancing the dewaterability of waste activated sludge were investigated. Capillary suction time (CST) was used to characterize sludge dewatering. Zeta potential, particle size distribution, three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy, fourier-transformed infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM) were employed to explore influencing mechanisms. The results indicated that the dewaterability was deteriorated with single thermal treatment, but significantly enhanced in the presence of Fe(II)-S(2)O(8)(2-) oxidation and further advanced together with thermal treatment. EEM and FT-IR analysis indicated that combined thermal and Fe(II)-S(2)O(8)(2-) oxidation pretreatment led to degrading of tyrosine and tryptophan protein-like substances in extracellular polymeric substances (EPS) and cleavage of linkages in polymeric backbone. SEM images further revealed the rupture of sludge flocs at the colloidal scale, which contributed to the release of EPS-bound water and interstitial water trapped between flocs, and subsequent enhanced dewaterability.