The development of hybrid heterostructure photocatalysts with enhanced visible light absorption capacity holds significant importance in environmental remediation. However, the challenge persists in exploiting strong visible-light responsive photocatalysts with both high efficiency and stability. Herein, we successfully synthesized a hybrid Z-scheme heterojunction of Bi2O3 and UiO-66-NH2 (Bi2O3/UiO-66-NH2) through a simple hydrothermal route. The visible light photocatalytic performance of Z-scheme Bi2O3/UiO-66-NH2 heterojunction is systematically evaluated for persistent antibiotic tetracycline hydrochloride (TC-HCl) both in the clean and real water matrix. All heterojunction catalysts exhibit superior photodegradation capabilities compared to pristine Bi2O3 and UiO-66-NH2. The optimal ratio of the two components heterojunction (BUN-150), in particular, demonstrates the highest removal efficiencies for TC-HCl (95 %) within a 90-min timeframe. This remarkable photocatalytic performance is credited to the Z-scheme charge transfer occurring at the interface of Bi2O3 and UiO-66-NH2 in Bi2O3/UiO-66-NH2 heterojunction. The active species experiments and electron paramagnetic resonance analyses are conducted to identify the active reactive species during the TC-HCl degradation (·OH, h+, and ·O2−), and a precise photocatalytic degradation mechanism is explained. Additionally, the photodegradation intermediates of TC-HCl are detected using the HPLC-MS analysis to explain the degradation pathways of TC-HCl. This research paves the way for the development of novel Z-scheme Bi2O3-based heterojunction catalysts for outstanding photocatalytic applications.