The enhancement of sludge dewaterability is of great importance for facilitating the sludge disposal during the operation of wastewater treatment plants. In this study, a novel oxidative conditioning approach was applied to enhance the dewaterability of waste activated sludge by the combination of zero-valent iron (ZVI) and peroxymonosulfate (PMS). It was found that the dewaterability of sludge was significantly improved after the addition of ZVI (0–4 g/g TSS) (TSS: total suspended solids) and PMS (0–1 g/g TSS). The optimal addition amount of ZVI and PMS was 0.25 g/g TSS and 0.1 g/g TSS, respectively, under which the capillary suction time of the sludge was reduced by approximately 50%. The decomposition of sludge flocs could contribute to the improved sludge dewaterability. Economic analysis demonstrated that the proposed conditioning process with ZVI and PMS was more economical than the ZVI + peroxydisulfate and the traditional Fenton conditioning processes.