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Photocatalyst is the core of photocatalysis and directly determines photocatalytic performance. However, low quantum efficiency and low utilization of solar energy are important technical problems in the application of photocatalysis. In this work, a series of polyoxometalates (POMs) [H₃PW₁₂O₄₀] (PW₁₂)-doped titanium dioxide (TiO₂) nanofibers modified with various amount of silver (Ag) nanoparticles (NPs) were prepared by utilizing electrospinning/photoreduction strategy, and were labelled as x wt% Ag/PW₁₂/TiO₂ (abbr. x% Ag/PT, x = 5, 10, and 15, respectively). The as-prepared materials were characterized with a series of techniques and exhibited remarkable catalytic activities for visible-light degradation tetracycline (TC), enrofloxacin (ENR), and methyl orange (MO). Particularly, the 10% Ag/PT catalyst with a specific surface area of 155.09 m²/g and an average aperture of 4.61 nm possessed the optimal photodegradation performance, with efficiencies reaching 78.19% for TC, 93.65% for ENR, and 99.29% for MO, which were significantly higher than those of PW₁₂-free Ag/TiO₂ and PT nanofibers. Additionally, various parameters (the pH of the solution, catalyst usage, and TC concentration) influencing the degradation process were investigated in detail. The optimal conditions are as follows: catalyst usage: 20 mg; TC: 20 mL of 20 ppm; pH = 7. Furthermore, the photodegradation intermediates and pathways were demonstrated by HPLC-MS measurement. We also investigated the toxicity of products generated during TC removal by employing quantitative structure-activity relationship (QSAR) prediction through a toxicity estimation software tool (T.E.S.T. Version 5.1.2.). The mechanism study showed that the doping of PW₁₂ and the modification of Ag NPs on TiO₂ broadened the visible-light absorption, accelerating the effective separation of photogenerated carriers, therefore resulting in an enhanced photocatalytic performance. The research provided some new thoughts for exploiting efficient and durable photocatalysts for environmental remediation. Full article