In this work, Fe(II) catalyzing sodium percarbonate (Fe(II)/SPC) was managed to facilitate waste activated sludge (WAS) dewatering for the first time. The results showed that after WAS was treated by 20 mg/g total suspended solids (TSS) Fe(II) and 50 mg/g TSS SPC, the water content of sludge cake (WCSC) by press filtration and capillary suction time (CST) dropped from 90.8% ± 1.6% and 96.1 ± 4.0 s (the control) to 55.6% ± 1.4% and 30.1 ± 2.5 s, respectively. The mechanism investigations indicated that four intermediates or products (i.e., •OH, H2O2, Fe(II), and Fe(III)) generated in the Fe(II)/SPC process were responsible for the improved WAS dewaterability, and •OH and Fe(III) were the two major contributors. It was found that •OH collapsed and fragmented extracellular polymeric substances, damaged cell wall and permeabilized cytoplasmic membrane, and transformed conformation of the extracellular proteins secondary structure via both affecting the hydrogen bond maintaining α-helix and cracking disulfide bond in cysteine residues while Fe(III), the oxidization product of Fe(II), decreased the surface electronegativity and water-affinity surface areas of WAS flocs. As a result, the bound water release, flocculability, surface hydrophobicity, drain capability, and flowability of WAS flocs were strengthened whereas the compact surface structure, colloidal forces, network strength, gel-like structure, and apparent viscosity of WAS flocs were weakened. In addition, Fe(II)/SPC process also reduced the recalcitrant organics and fecal coliforms in sludge, which facilitated land application of dewatered sludge. The findings acquired in this work not only deepens our understanding of Fe(II)/SPC-involved WAS treatment process but also may guide engineers to develop both effective and promising strategies to better condition WAS for dewatering in the future.