In the study, we successfully decorated MnFe2O4 on BiVO4 to highly improve its photocatalytic activity for degradation of tetracycline as well as its magnetically recovery. The decoration of MnFe2O4 on BiVO4 led to formation of MnFe2O4/BiVO4 Z scheme heterojunction to effectively prevent the charge recombination in each material. Upon visible light, the MnFe2O4/BiVO4 heterojunction produced significant available amounts of e− and h+ existing in the conduction band of the MnFe2O4 and the valence band of the BiVO4, respectively. These produced e− on the conduction band of the MnFe2O4, which reduction potential was approximately −0.41 eV, exhibited strong reduction potential reducing oxygen to produce •O2− radicals while h+ on the valence band of the BiVO4, which oxidation potential was 2.77 eV, showed strong oxidation potential oxidizing water and hydroxyl groups to produce •OH radicals. These generated active oxygen radicals effectively degraded TC in water (~92%). The used photocatalysts were easily recovered from photocatalytic suspension using an external magnet due to high magnetically activity of the MnFe2O4, which tightly bonded with BiVO4 in the MnFe2O4/BiVO4 heterojunction. Finally, the recovered MnFe2O4/BiVO4 heterojunction was very active and stable for tetracycline degradation in long-term process.