The Z-scheme MIL-100(Fe)/PANI composite photocatalysts were facilely prepared from MIL-100(Fe) and polyaniline (PANI) by ball-milling, and were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), UV–visible diffuse-reflectance spectrometry (UV–vis DRS), X-ray photoelectron spectroscopy (XPS) and photoluminescence emission spectrometry (PL). The photocatalytic activities of MIL-100(Fe)/PANI composites were investigated via tetracycline degradation and hexavalent chromium reduction in aqueous solution under the irradiation of white light. The results revealed that the MIL-100(Fe)/PANI composite photocatalysts exhibited outstanding photocatalytic activities toward Cr(VI) reduction and tetracycline decomposition. The effects of pH and coexisting ions on the photocatalytic Cr(VI) reduction were investigated. As well, the primary active species were identified via electron spin resonance (ESR) determination. A possible Z-scheme photocatalyst mechanism was proposed and verified. Finally, MIL-100(Fe)/PANI composites demonstrated good reusability and stability in water solution, implying potentially practical applications for real wastewater treatment. Display omitted •The Z-scheme MIL-100(Fe)/PANI (MPx%) photocatalysts were facilely synthesized.•MP9% exhibited superior photocatalytic activity toward Cr(VI) and tetracycline.•MIL-100(Fe)/PANI composites demonstrated good reusability and stability.•Z-scheme mechanism was proposed to clarify the improved photocatalytic activity.