AbstractA new type of modified catalyst was prepared by a silver ammonia‐assisted precipitation method through a custom‐built electrochemical reactor, and the catalytic degradation of the azo dye methyl orange was studied under the synergistic effect of visible light. The optimum doping ratio for the loading of graphene oxide (GO) is 1.0 %. Under the optimum conditions, the degradation rate of Ag3PO4/GO/NiFe2O4 to methyl orange is 97.56 % when the light reaction time is 50 min. After three cycles, the degradation rate of methyl orange by Ag3PO4/GO/NiFe2O4 is 94.47 %. Through the free radical capture experiment, it is known that the contribution degree of the main active substances in the photocatalytic degradation of methyl orange is h + >⋅O2− >⋅OH. By forming a Z‐type heterojunction between Ag3PO4 and NiFe2O4, the recombination probability of photogenerated carriers is greatly reduced, and the stability of Ag3PO4 is improved.