The construction of Z-scheme charge transfer pathways simulating natural photosynthesis is considered a promising method for improving reaction driving forces. Here, we modified the surface of titanium doped Fe2O3 (Ti-Fe2O3) nanorods with NH2-MIL-125(Ti) (Ti-MOFs) and a promising organic-inorganic hybrid Z-scheme NH2-MIL-125(Ti)/Ti-Fe2O3 was successfully prepared. At 1.23 V vs. RHE, the photocurrent density of the composite photoanode reaches 2.67 mA/cm2, which is 5 times higher than that of Ti-Fe2O3. The results of surface photovoltage, ESR and fs-TAS indicate that this improvement is mainly due to the effective Z-scheme charge transfer mechanism providing a strong driving force for charge separation and transport, greatly suppressing carrier recombination and allowing carriers with strong oxidation ability to participate in water oxidation. Meanwhile, NH2-MIL-125(Ti) can enhance light absorption and reduce the surface defect state of Ti-Fe2O3. This study not only provides a feasible approach for the photoanode water splitting of traditional inorganic semiconductor/MOF based heterostructures, but also provides rich and effective means for revealing Z-scheme charge transfer mechanism in depth.