The invention relates to a hydrolytic acidification-catalyzed iron/anaerobic-aerobic biological dephosphorization coupling process which is realized by a hydrolytic acidification-catalyzed iron/anaerobic-aerobic biological dephosphorization coupling device. The device is composed of a hydrolytic acidification tank, an anaerobic tank and a catalyzed iron filler therein, an aerobic tank and a precipitation tank which are sequentially connected. The process specifically comprises the following steps: sewage is fed into the hydrolytic acidification tank, and the hydraulic retention time is controlled to be 2-6 hours; the effluent water after hydrolytic acidification reaction is fed into the anaerobic tank, sludge in the anaerobic tank is refluxed by the aerobic tank, the reflux liquid brings dissolved oxygen to destroy the anaerobic phosphorus release environment of phosphorus-accumulating bacteria, and the catalyzed iron can effectively remove the dissolved oxygen and simultaneously form ferrous ions; the effluent water of the anaerobic tank passes through the aerobic tank, and the ferrous ions are oxidized to become ferric ions and be combined with phosphate ions to form precipitates, thus achieving dephosphorization effect; and the effluent water of the aerobic tank is precipitated in the precipitation tank, the effluent water is discharged, and part of sludge is refluxed to the anaerobic tank. The process provided by the invention greatly makes up the limitation of the current biological dephosphorization process, and has favorable application prospects.