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

Abstract The photoconversion of CO 2 into valuable chemical products using solar energy is a promising strategy to address both energy and environmental challenges. However, the strongly adsorbed CO 2 frequently impedes the seamless advancement of the subsequent reaction by significantly increasing the reaction activation energy. Here, we present a BiFeO 3 material with lattice strain that collaboratively regulates the d/p‐2π* orbitals hybridization between metal sites and *CO 2 as well as *COOH intermediates to achieve rapid conversion of solidly adsorbed CO 2 to critical *COOH intermediates, accelerating the overall CO 2 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 CO 2 , and continuous internal electrons are rapidly transferred to the reaction sites and injected into the surface *CO 2 and *COOH under the condition of illumination, which promotes the rapid formation and stability of *COOH. Certainly, the performance of CO 2 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 CO 2 .