This study introduces a contact-electro-catalytic approach for CO₂ reduction from ambient air, achieving a CO Faradaic efficiency of 96.24%. The method utilizes a triboelectric nanogenerator (TENG) consisting of electrospun polyvinylidene fluoride (PVDF) loaded with single Cu atoms-anchored polymeric carbon nitride (Cu-PCN) catalysts and quaternized cellulose nanofibers (CNF). The Cu-PCN catalyst enriches electrons during contact electrification, facilitating electron transfer upon contact with CO₂ adsorbed on quaternized CNF. This setup enables efficient CO₂ capture at low concentrations, leading to a CO production rate of 33 μmol g⁻¹ h⁻¹, outperforming state-of-the-art air-based CO₂ reduction technologies. The mechanism involves the strong adsorption of CO₂ on quaternized CNF, which facilitates electron transfer from Cu-PCN to CO₂, resulting in the formation of CO. The study highlights the potential of this technique for reducing atmospheric CO₂ emissions and advancing chemical sustainability.This study introduces a contact-electro-catalytic approach for CO₂ reduction from ambient air, achieving a CO Faradaic efficiency of 96.24%. The method utilizes a triboelectric nanogenerator (TENG) consisting of electrospun polyvinylidene fluoride (PVDF) loaded with single Cu atoms-anchored polymeric carbon nitride (Cu-PCN) catalysts and quaternized cellulose nanofibers (CNF). The Cu-PCN catalyst enriches electrons during contact electrification, facilitating electron transfer upon contact with CO₂ adsorbed on quaternized CNF. This setup enables efficient CO₂ capture at low concentrations, leading to a CO production rate of 33 μmol g⁻¹ h⁻¹, outperforming state-of-the-art air-based CO₂ reduction technologies. The mechanism involves the strong adsorption of CO₂ on quaternized CNF, which facilitates electron transfer from Cu-PCN to CO₂, resulting in the formation of CO. The study highlights the potential of this technique for reducing atmospheric CO₂ emissions and advancing chemical sustainability.