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 WO3nanoparticles 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.