The electrochemical reduction of CO 2 (ERCO 2 ) into economically valuable chemicals is one of the most promising ways to achieve carbon neutrality. Perovskite materials have shown potential applications in high-temperature catalysis and photocatalysis due to their unique structure, but their catalytic performance during the aqueous ERCO 2 has rarely been investigated. In this study, we developed an efficient YbBiO 3 perovskite catalyst (YBO@800) for CO 2 conversion to formate, with a maximum faradaic efficiency of 98.3% at -0.9 V RHE , as well as a considerable faradaic efficiency (>90%) over a wide potential range (from -0.8 to -1.2 V RHE ). Further analyses demonstrated that the structural evolution of YBO@800 occurred during the ERCO 2 process, and the subsequent construction of the Bi/YbBiO 3 heterostructure played a significant role in optimizing the rate-determining step of the ERCO 2 . This work inspires the development of perovskite catalysts for the ERCO 2 and provides insight into the influence of the surface reconstruction of catalysts on their electrochemical performance.