α–Fe 2 O 3 is a promising photoanode that can be used for solar‐driven photoelectrochemical (PEC) water splitting. However, due to low carrier separation efficiency and slow water oxidation kinetics, the PEC performance of Ti–Fe 2 O 3 is still severely hindered. Here, a novel inorganic–organic hybrid composite photoanode is prepared by depositing NH 2 –materials of institute Lavoisier (MIL)–53(FeCo) cocatalyst on the surface of Ti–Fe 2 O 3 using solvothermal method. In the results, it is shown that the Ti–Fe 2 O 3 /NH 2 –MIL–53(FeCo) photoanode has a high photocurrent density (3.0 mA cm −2 at 1.23 V vs reversible hydrogen electrode (RHE), which is 5.1 times that of bare Ti–Fe 2 O 3 , and the initial potential of water oxidation also undergoes a negative change of about 100 mV. The separation efficiency of Ti–Fe 2 O 3 /NH 2 –MIL–53(FeCo) is significantly enhanced, and the charge injection efficiency increases from 17.6% to 68% at 1.23 V versus RHE. In the further research, it is suggested that the excellent PEC performance of Ti–Fe 2 O 3 /NH 2 –MIL–53(FeCo) may be attributed to an increase in carrier density, prolonged carrier recombination time, and an increase in exposed reactive sites. In this study, a new understanding for the design of Ti–Fe 2 O 3 photoanodes with superior PEC performance based on metal organic framework modification is provided.