With the semiconductor modified oxygen evolution (OER) catalyst as the photoanode, the solar energy can be fully utilized, and the synergistic reaction makes the OER catalyst play a great role in the photochemical (PEC) water decomposition. Herein, we adopted a one-step hydrothermal method to introduce TiO2 to form heterojunction as photoanode in a well-known NiFe-LDH electrocatalyst, which contributes to carrier separation and transfer efficiency, thereby speeding up the water oxidation reaction kinetics. Benefiting from the TiO2/Ni4Fe6-LDH heterojunctions, the TiO2/ Ni4Fe6-LDH shows an overpotential of 371 mV @30 mA cm−2 and a Tafel slope of 131.36 mV/dec under illumination, which is better than Ni4Fe6-LDH and TiO2. The comparison experiment of oxygen evolution efficiency showed that the polarization current density of TiO2/Ni4Fe6-LDH reached 12 mA cm−2 under the illumination voltage of 1.72 V, which was twice the current density under the non-illumination condition. Surface electronic structure analysis shows that these excellent OER performance are largely due to the introduction of TiO2, which not only enables Ni4Fe6-LDH surface to have more oxygen vacancy, increase photoanode conductivity and accelerate reaction electron conduction, but also accelerates hole capture and enhances OER reaction kinetics. This synergistic effect between semiconductor and OER catalyst provides more ideas for realizing efficient and stable photoelectrochemical water oxidation.