Unlike many studies on the preparation of Z-scheme heterojunctions by doping precious metals, in this paper we first prepared a core-shell material obtained by C doping in ZnO and then composite with MnO2 to form a heterojunction; that is, a low-cost and highly catalytic ternary composite catalyst was prepared by a simple hydrothermal reaction. Meanwhile, a large amount of experimental data have enabled the heterostructure type as well as the mechanism of photocatalytic performance to be fully demonstrated. It is proven that C as an intermediate medium achieves electron transport while making up the deficiency of ZnO, and constitutes an all-solid state Z-scheme heterojunction, which enables the rapid transfer of photogenerated electron pairs and visible light irradiation to the stream to improve the photocatalytic performance of the composite photocatalyst. In terms of examination of degradation performance, this catalyst showed a high photodegradation rate of tetracycline hydrochloride (TC) of 92.6% within 60 min, and the surface ZnO-C/MnO2 catalysts also showed good degradation effect on practical petrochemical wastewater in CODcr degradation experiments.