Enhancing d/p‐2π* Orbitals Hybridization via Strain Engineering for Efficient CO ₂ Photoreduction

The photoconversion of CO₂ into valuable chemical products using solar energy is a promising strategy to address both energy and environmental challenges. However, the strongly adsorbed CO₂ frequently impedes the seamless advancement of the subsequent reaction by significantly increasing the reaction activation energy. Here, we present a BiFeO₃ material with lattice strain that collaboratively regulates the d/p-2π* orbitals hybridization between metal sites and *CO₂ as well as *COOH intermediates to achieve rapid conversion of solidly adsorbed CO₂ to critical *COOH intermediates, accelerating the overall CO₂ reduction kinetics. Quasi in situ X-ray photoelectron spectroscopy and in situ Fourier Transform infrared spectroscopy combined with theoretical calculation reveals that the optimized Fe sites enhance the adsorption and activation effect of CO₂, and continuous internal electrons are rapidly transferred to the reaction sites and injected into the surface *CO₂ and *COOH under the condition of illumination, which promotes the rapid formation and stability of *COOH. Certainly, the performance of CO₂ photoreduction to CO is improved by 12.81-fold compared with the base material. This work offers a new perspective for the rapid photoreduction process of strongly adsorbed CO₂.