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In this study, a Z-Scheme WO₃/CoO p-n heterojunction with a 0D/3D structure was designed and prepared via a simple solvothermal approach to remove the combined pollution of tetracycline and heavy metal Cr(VI) in water. The 0D WO₃ nanoparticles adhered to the surface of the 3D octahedral CoO to facilitate the construction of Z-scheme p-n heterojunctions, which could avoid the deactivation of the monomeric material due to agglomeration, extend the optical response range, and separate the photogenerated electronhole pairs. The degradation efficiency of mixed pollutants after a 70 min reaction was significantly higher than that of monomeric TC and Cr(VI). Among them, a 70% WO₃/CoO heterojunction had the best photocatalytic degradation effect on the mixture of TC and Cr(VI) pollutants, and the removing rate was 95.35% and 70.2%, respectively. Meanwhile, after five cycles, the removal rate of the mixed pollutants by the 70% WO₃/CoO remained almost unchanged, indicating that the Z-scheme WO₃/CoO p-n heterojunction has good stability. In addition, for an active component capture experiment, ESR and LC-MS were employed to reveal the possible Z-scheme pathway under the built-in electric field of the p-n heterojunction and photocatalytic removing mechanism of TC and Cr(VI). These results offer a promising idea for the treatment of the combined pollution of antibiotics and heavy metals by a Z-scheme WO₃/CoO p-n heterojunction photocatalyst, and have broad application prospects: boosted tetracycline and Cr(VI) simultaneous cleanup over a Z-scheme WO₃/CoO p-n heterojunction with a 0D/3D structure under visible light.