<p>Electrochemical CO₂ reduction to formate offers a sustainable route, but achieving high selectivity on transition metal catalysts remains a significant challenge, which is typically favored on <i>p</i>-block metals. Here, we demonstrate that chalcogenide-stabilized cuprous enables near-complete formate selectivity through a charge redistribution mechanism induced by chalcogenides. Using in situ X-ray absorption spectroscopy, high-energy-resolution fluorescence-detected XAS, Raman, and infrared spectroscopy, we reveal that Cu-chalcogen interactions stabilize Cu⁺, preventing over-reduction to Cu⁰ and thereby modulating CO₂ adsorption and intermediate binding. This stabilization enhances the *OCHO pathway, shifting product distribution entirely toward formate. CuS exhibits the highest selectivity, achieving a notable 90% faradaic efficiency at −0.6 V and an ampere-scale formate partial current of 1.36 A, demonstrating industrial feasibility. In contrast, CuO, lacking a charge redistribution effect, promotes a mixture of CO and C2 products, underscoring the critical role of chalcogenides in steering product selectivity. This work provides fundamental insights into charge redistribution in CO₂RR and introduces a catalyst design strategy leveraging chalcogen-induced electronic modifications for scalable formate production.</p>