The charge separation of photogenerated carriers in the photo-self-Fenton system still limits its ability to remove organic contaminants.To overcome this limitation, a novel MOF/COF direct Z-scheme-based photo-self-Fenton system (MIL-100(Fe)/TpPa-1 COF, MT2) was designed and synthesized for removing tetracycline hydrochloride (TC) from water.As a result, 91 % of TC (20 mg L-1, 100 mL) was removed by MT2 (0.08 g L-1) within 120 min, driven by improved charge separation and the synergistic effects of h+, ·OH, and ·O-2.Theor. calculations confirmed the improved charge dynamics within the heterojunction, supporting efficient photocatalytic degradationLC-MS anal. and DFT calculations revealed the potential degradation intermediates and pathways of TC.TC was found to significantly inhibit wheat seedling growth and chlorophyll production, while its intermediates exhibited negligible inhibitory effects.Addnl., the ecotoxicity of TC was significantly reduced, as evidenced by the decreased inhibition zones for Escherichia coli and Staphylococcus aureus.Thus, the in-situ photo-Fenton composite shows great potential for practical applications in antibiotics removal.