Ultraviolet (UV) assisted zero-valent iron (ZVI)-activated sodium persulfate (PDS) oxidation (UV-ZVI-PDS) was used to treat waste activated sludge (WAS) in this study. The dewaterability performance and mechanism of WAS dewatering were analyzed. The results showed that UV-ZVI-PDS can obtain better sludge dewatering performance in a wide pH range (2.0-8.0). When the molar ratio of ZVI/PDS was 0.6, UV was 254nm, PDS dosage was 200 mg/g TS (total solid), pH was 6.54, reaction time was 20 min, the CST (capillary suction time) and SRF (specific resistance to filtration) were decreased by 64.0% and 78.2%, respectively. The molar ratio of ZVI/PDS used in this paper is much lower than that of literatures, and the contents of total Fe and Fe2+ in sludge supernatant remained at a low level, as 3.7 mg/L and 0.0 mg/L. The analysis of extracellular polymeric substances (EPS), scanning electron microscope (SEM) and particle size distribution showed that the EPS could be effectively destroyed by UV-ZVI-PDS, the sludge flocs broken down into smaller particles, cracks and holes appeared, and then the bound water was released. At the same time, the highly hydrophilic tightly bound-EPS (TB-EPS) were converted into loosely bound EPS (LB-EPS) and soluble EPS (S-EPS). During sludge pretreated by UV-ZVI-PDS, positively charged ions, such as Fe2+, Fe3+ and H+, produced in the reaction system could reduce the electronegativity of sludge surface, promote sludge particles aggregation, and then enhanced the sludge dewaterability.