Rational design of high-performance catalysts for CO2 electroreduction is crucial for achieving carbon neutrality, yet effective modification strategies remain scarce. In this study, we present the microwave heating approach to incorporate La3+ ions into Sn-based perovskite oxides, significantly enhancing their electrocatalytic performance for the reduction of CO2 to formate. Through comprehensive characterization techniques, including X-ray photoelectron spectroscopy, synchrotron radiation X-ray absorption spectroscopy, electrochemical measurements (Tafel analysis and impedance spectroscopy), and density functional theory calculations, we demonstrate that La3+ substitution effectively modulates the Sn-O bond distance in BaSnO3. This structural modification induces local charge density enrichment, facilitates CO2 adsorption, and enhances electron transfer kinetics, resulting in a substantial improvement in the formate Faradaic efficiency. In situ Raman spectroscopic analysis and postreaction XPS characterization confirmed the structural integrity of the perovskite framework and the preservation of Sn valence states under negative potentials. This work provides fundamental insights into the CO2 reduction reaction mechanism on perovskite electrocatalysts and establishes a framework for the design of advanced tin-based electrocatalysts.