Developing high-efficiency photocatalysts for CO₂ photoreduction is one of the potential solutions to address both energy and pollution issues. In this study, α-Fe₂O₃ modified La₂Ti₂O₇ was successfully synthesized with intimate contact between La₂Ti₂O₇ and α-Fe₂O₃, greatly facilitating the carrier separation and transfer during the photocatalytic reaction. The activity and stability for photocatalytic CO₂ reduction over α-Fe₂O₃/La₂Ti₂O₇ were significantly improved as compared with the La₂Ti₂O₇ substrate. The optimized 3% α-Fe₂O₃/ La₂Ti₂O₇ composite showed excellent CO₂ reduction activity after 5 h consecutive illumination, and the total utilized photoelectron number (UPN) reached 7.76 μmol, which was about 4.4 times higher than that of the pristine La₂Ti₂O₇. The steady-state photoluminescence spectra, time-resolved photoluminescence spectra (TRPL) and photocurrent response results showed that the improved charge separation efficiency was the key factor to enhance the photocatalytic activity. This work provides novel insights into the design and fabrication of photocatalysts of high performance for CO₂ reduction for solar-to-energy applications.