During wet weather, sewer overflow pollution can pose a serious threat to surface water. In order to reduce the impact of overflow discharge on receiving waters, ferric chloride (Fe(Ⅲ))/potassium ferrate (Fe(Ⅵ))/polyacrylamide (PAM) coagulation (Fe(Ⅲ)/Fe(Ⅵ)/PAM) combined with sodium hypochlorite (NaClO) oxidation was proposed. Different combinations were constructed, including pre-oxidation coagulation (NaClO-Fe(Ⅲ)/Fe(Ⅵ)/PAM), pre-coagulation oxidation (Fe(Ⅲ)/Fe(Ⅵ)/PAM-NaClO), and synchronous coagulation oxidation (NaClO+Fe(Ⅲ)/Fe(Ⅵ)/PAM). The combined processes achieved efficient removal of conventional contaminants, and the produced byproducts were controlled, especially in the NaClO-Fe(Ⅲ)/Fe(Ⅵ)/PAM. The obvious discrepancy in the sulfamethoxazole (SMX) removal was observed in different processes. NaClO affected the distribution of hydrolyzed iron species, and the proportion of active iron in the NaClO-Fe(Ⅲ)/Fe(Ⅵ)/PAM significantly increased. More complexation sites were generated in the NaClO-Fe(Ⅲ)/Fe(Ⅵ)/PAM, which can complex with the coagulant and then effectively transfer to the flocs. The composition of the flocs further confirmed the differences in coagulation characteristics. The generated·OH played a crucial role in SMX removal in the NaClO+Fe(Ⅲ)/Fe(Ⅵ)/PAM, and ClO·was responsible for partial removal of ammonia nitrogen (NH4+-N). The contribution of high-valent iron species was confirmed, and the introduction of NaClO promoted the generation of iron species. This study may provide an ideal for overflow treatment to improve the urban water environment.