Efficient and deep degradation for organic contaminants in the absence of externally supplied H2O2 is still a challenge and research hotspot for photo-Fenton catalysis. In this work, a novel Ti3C2 MXene/MIL-100(Fe) hybrid via Fe-protoporphyrin bridging was proposed to in-situ generate H2O2 for photo-Fenton catalytic degradation of thiacloprid (TCL). The generated Schottky junction between MXene and MIL-100(Fe) and biomimetic oxygen-carrying from Fe-protoporphyrin constructed a synergistic system to promote H2O2 generation and photo-Fenton reaction. As expected, MXene/MIL-100(Fe) exhibited 12 times higher of H2O2 generation rate (reaching 1175.2 μmol/L under air-bubble), and 24 times of degradation rate and 3.7 times of mineralization rate for TCL compared to MIL-100(Fe). In addition, MXene/MIL-100(Fe) possessed 21–60 times higher TCL degradation rate than many of reported photo-Fenton catalysts in H2O2-free system. MXene/MIL-100(Fe) realized > 80 % TOC removal of TCL (80 mg/L) within 120 min, and exhibited excellent catalytic stability (>97 % TCL degradation) for 10 successive reuses.