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Metal–organic frameworks (MOFs) are new porous materials composed of metal centers and organic ligand bridges, which received great attention in the field of photocatalysis. In this work, Ag₂CrO₄@MIL–125(Ti)–NH₂ (denoted as AgCr@M125) Z–scheme heterojunctions were synthesized via a simple microemulsion method, by which highly dispersed nano–sized Ag₂CrO₄ can be anchored uniformly on the surfaces of porous MIL–125(Ti)–NH₂ (denoted as M125). Compared with pure M125 and Ag₂CrO₄, the as–prepared AgCr@M125 hybrids show significant photocatalytic efficiency against inactivated <i>Staphylococcus aureus</i> (<i>S. aureus</i>), reaching over 97% inactivation of the bacteria after 15 min of visible light irradiation. Notably, the photocatalytic activity of the obtained 20%AgCr@M125 is about 1.75 times higher than that of AgCr–M125, which was prepared via a traditional precipitation method. The enhanced photocatalytic antibacterial activity of the AgCr@M125 photocatalytic system is strongly ascribed to a direct Z–scheme mechanism, which can be carefully discussed based on energy band positions and time–dependent electron spin response (ESR) experiments. Our work highlights a simple way to enhance the antibacterial effect by coupling with Ag₂CrO₄ and M125 via a microemulsion–assisted strategy and affords an ideal example for developing MOFs–based Z–scheme photocatalysts with excellent photoactivity.