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B 4 C 12 achieves a rapid and stable CO 2 adsorption with a novel η3(O, C, O)-CO 2 configuration, and a small limiting potential for CO2RR producing HCOOH associating with suppressed HER. [Display omitted] The electrochemical reduction of CO 2 (CO2RR) to formic acid (HCOOH) is a promising approach to harness renewable energy for the production of value-added chemicals and contribute to carbon cycling. The search for cost-effective and efficient metal-free electrocatalysts is critical for realizing industrial applications. However, limited literature is available on this topic, primarily because the significant challenge of efficiently activating inert CO 2 remains unresolved. In this study, we have designed and applied a novel boron carbide (B 4 C 12) monolayered cage as an electrocatalyst for CO2RR to produce HCOOH. B 4 C 12 exhibits exceptional electronic, dynamic, and thermodynamic stability. Through comprehensive density functional theory computations, we have observed that B 4 C 12 rapidly and stably adsorbs CO 2 in a unique η3(O, C, O)-CO 2 configuration, resulting in excellent CO2RR activity with a low limiting potential (–0.38 V) and suppressed hydrogen evolution reaction. Our mechanistic investigations reveal that B 4 C 12 donates electrons to facilitate the bending of CO 2 , anchoring it onto the curved surface effectively. Additionally, the C atom in the η3(O, C, O)-CO 2 configuration attracts H+ + e− pairs through its active p electron, leading to the observed low limiting potential. This study not only successfully designs a novel class of metal-free electrocatalysts but also provides a promising strategy for advancing CO2RR research in the future. [ABSTRACT FROM AUTHOR]