Preparation of CeO2/PbFe12O19 (CO/PFO) heterojunction photocatalysts with the different CO contents as visible‐light photocatalysts were synthesized by a polyacrylamide gel route combined with a low temperature sintering technique. A variety of characterization techniques have been used to confirm that the CO/PFO heterojunction photocatalysts contain only Ce, Pb, Fe and O elements, which also indicates that the special interfacial contact between CO and PFO is formed and there are a large number of oxygen vacancies and interfacial defects in CO/PFO heterojunction photocatalysts. The coupling of CO and PFO enhances the optical absorption coefficients of CO and PFO and slightly decreases the optical band gap (Eg) of the host lattice (PFO). Rhodamine B (RhB), phenol, bisphenol A (BPA) and oxytetracycline hydrochloride (OTC‐HCl) were used as target degradation pollutants to investigate the degradation preference of CO/PFO heterojunction photocatalysts. The degradation percentages of the RhB, Phenol, BPA and OTC‐HCl are 20.35 %, 38.77 %, 18.11 % and 75.32 %, respectively. The results showed that the hydroxyl radical played a dominant role in the degradation of pollutants by the CO/PFO heterojunction photocatalysts and preferred to degrade −C=O and −CONH2. This new idea will provide technical support for cutting functional groups of pollutants purposefully.