<p>The accumulation of tetracycline antibiotics in water environments can lead to the emergence of antibiotic-resistant bacteria and resistance genes, posing a potential threat to ecosystems and human health. Therefore, the development of cost-effective and efficient methods for the remediation of antibiotic wastewater has become a current research hotspot. In this study, a novel photocatalyst, UiO-66-CA-Cu (CA was the abbreviation for “citric acid”), was prepared by two-step functionalization modification of the MOF material (University of Oslo-66, abbreviated as UiO-66). Under irradiation of simulated sunlight, UiO-66-CA-Cu-led photocatalysis and peroxymonosulfate (PMS) activation co-degradation system achieved 93.3% (<i>k</i> = 0.04712&#xa0;min⁻¹) removal efficiency of tetracycline hydrochloride (20&#xa0;mg/L, 50&#xa0;mL) within 60&#xa0;min. The functional modification was used to optimize the local environment of the parent MOF. The asymmetry of the Zr–O cluster structure introduced by CA could effectively improve the separation efficiency of photogenerated carrier in the material, and the introduced Cu²⁺ ions could be used as the activation site to further enhance the material’s activation ability to PMS.</p> Graphical Abstract <p>In this work, a novel photocatalyst, UiO-66-CA-Cu (CA was the abbreviation for “citric acid”), was prepared by two-step functionalization modification of the MOF material (UiO-66). Under simulated sunlight irradiation, the degradation system constructed by the photocatalyst UiO-66-CA-Cu coupled with peroxymonosulfate (PMS) activation could achieve efficient removal of tetracycline hydrochloride (removal efficiency: 93.3%, k = 0.04712 min^-1). In addition, we systematically investigated the effects of PMS concentration, photocatalyst concentration and initial pH value on the degradation performance over this system, and further proposed the possible degradation mechanism.</p> <p></p>