摘要：To solve the excessive emission of CO_(2) caused by the excessive use of fossil fuels and the corre‐sponding environmental problems,such as the greenhouse effect and climate warming,electrocat‐alytic CO_(2) reduction to liquid fuel with high selectivity is of huge significance for energy conversion and *** has been considered as a promising and attractive metal for the reduction of CO_(2) to ***,the current issues,such as low selectivity and current activity,largely limit the industrial application for electrocatalytic CO_(2) reduction,the design optimization of the catalyst structure and composition is extremely ***,we develop a facile strategy to regulate surface In–O of In@InO_(x) core‐shell nanoparticles and explore the structure‐performance relation‐ship for efficient CO_(2)‐to‐formate conversion though air calcination and subsequent in situ electro‐chemical reconstruction,discovering that the surface In–O is beneficial to stabilize the CO_(2) interme‐diate and generate *** optimized AC‐In@InO_(x)‐CNT catalyst exhibits a C1 selectivity up to 98%and a formate selectivity of 94%as well as a high partial formate current density of 32.6 mA cm^(-2).Furthermore,the catalyst presents an excellent stability for over 25 h with a limited activity decay,outperforming the previously reported In‐based *** insights may open up op‐portunities for exploiting new efficient catalysts by manipulating their surface.