The efficient removal of persistent organic pollutants (POPs) in natural waters is vital for human survival and sustainable development. Photocatalytic degradation is a feasible and cost-effective strategy to completely disintegrate POPs at room temperature. Herein, we develop a series of direct Z-scheme BiOIO 3 /AgIO 3 hybrid photocatalysts via a facile deposition-precipitation method. Under natural sunlight irradiation, the light intensity of which is ∼40 mW/cm 2 , a considerable rate constant of 0.185 min -1 for photodecomposing 40 mg/L MO is obtained over 0.5 g/L Bi@Ag-5 composite photocatalyst powder, about 92.5 and 5.3 times higher than those of pristine AgIO 3 and BiOIO 3 . The photoactivity of Bi@Ag-5 for photodecomposing MO under natural sunlight illumination surpasses most of the reported photocatalysts under Xe lamp illumination. After natural sunlight irradiation for 20 min, 95% of MO, 82% of phenol, 78% of 2,4-DCP, 54% of ofloxacin, and 88% of tetracycline hydrochloride can be photodecomposed over Bi@Ag-5. Relative to the commercial photocatalyst TiO 2 (P25), Bi@Ag-5 exhibits greatly higher photoactivity for the treatment of MO-phenol-tetracycline hydrochloride mixture pollutants in the scale-up experiment of 500 mL of solution, decreasing COD, TOC, and chromaticity value by 52, 19, and 76%, respectively, after natural sunlight irradiation for 40 min. The photodegradation process and mechanism of MO have been systematically investigated and proposed. This work provides an archetype for designing efficient photocatalysts to remove POPs.