A contact-electro-catalytic approach for CO₂ reduction from ambient air is introduced, achieving a CO Faradaic efficiency of 96.24%. The method utilizes a triboelectric nanogenerator (TENG) composed 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 catalysts enrich electrons during contact electrification, facilitating electron transfer to CO₂ adsorbed on quaternized CNF. The strong adsorption of CO₂ on quaternized CNF enables efficient CO₂ capture at low concentrations, allowing the CO₂ reduction reaction in ambient air. This technique achieves a superior CO yield of 33 μmol g⁻¹ h⁻¹, offering a solution for reducing airborne CO₂ emissions while advancing chemical sustainability. The study highlights the potential of contact-electro-catalysis for CO₂ reduction, which leverages mechanical energy to generate electrical energy through triboelectric nanogenerators. This approach avoids the high energy consumption and expensive catalysts of traditional methods, making it a promising solution for sustainable CO₂ reduction. The mechanism involves the adsorption of CO₂ on quaternized CNF, followed by electron transfer to the CO₂ molecules facilitated by Cu-PCN catalysts. The unique combination of quaternized CNF and Cu-PCN enables efficient CO₂ reduction even in low CO₂ concentrations, such as ambient air. The study demonstrates the effectiveness of the contact-electro-catalytic system in reducing CO₂ to CO with high efficiency and stability. The system shows excellent performance under high humidity conditions, with a CO yield of 33 μmol g⁻¹ h⁻¹. The mechanism involves the adsorption of CO₂ on quaternized CNF, followed by electron transfer to the CO₂ molecules facilitated by Cu-PCN catalysts. The system is also stable under cyclic conditions, maintaining high CO yields over multiple cycles. The study provides a promising solution for reducing atmospheric CO₂ emissions and advancing sustainable chemical technologies. The contact-electro-catalytic approach offers a novel strategy for CO₂ reduction, combining the advantages of mechanical energy harvesting and efficient catalytic processes. The results demonstrate the potential of this method for real-world applications, including carbon capture and utilization in air environments. The study highlights the importance of quaternized CNF and Cu-PCN in enabling efficient CO₂ reduction, offering a pathway for further advancements in sustainable energy technologies.A contact-electro-catalytic approach for CO₂ reduction from ambient air is introduced, achieving a CO Faradaic efficiency of 96.24%. The method utilizes a triboelectric nanogenerator (TENG) composed 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 catalysts enrich electrons during contact electrification, facilitating electron transfer to CO₂ adsorbed on quaternized CNF. The strong adsorption of CO₂ on quaternized CNF enables efficient CO₂ capture at low concentrations, allowing the CO₂ reduction reaction in ambient air. This technique achieves a superior CO yield of 33 μmol g⁻¹ h⁻¹, offering a solution for reducing airborne CO₂ emissions while advancing chemical sustainability. The study highlights the potential of contact-electro-catalysis for CO₂ reduction, which leverages mechanical energy to generate electrical energy through triboelectric nanogenerators. This approach avoids the high energy consumption and expensive catalysts of traditional methods, making it a promising solution for sustainable CO₂ reduction. The mechanism involves the adsorption of CO₂ on quaternized CNF, followed by electron transfer to the CO₂ molecules facilitated by Cu-PCN catalysts. The unique combination of quaternized CNF and Cu-PCN enables efficient CO₂ reduction even in low CO₂ concentrations, such as ambient air. The study demonstrates the effectiveness of the contact-electro-catalytic system in reducing CO₂ to CO with high efficiency and stability. The system shows excellent performance under high humidity conditions, with a CO yield of 33 μmol g⁻¹ h⁻¹. The mechanism involves the adsorption of CO₂ on quaternized CNF, followed by electron transfer to the CO₂ molecules facilitated by Cu-PCN catalysts. The system is also stable under cyclic conditions, maintaining high CO yields over multiple cycles. The study provides a promising solution for reducing atmospheric CO₂ emissions and advancing sustainable chemical technologies. The contact-electro-catalytic approach offers a novel strategy for CO₂ reduction, combining the advantages of mechanical energy harvesting and efficient catalytic processes. The results demonstrate the potential of this method for real-world applications, including carbon capture and utilization in air environments. The study highlights the importance of quaternized CNF and Cu-PCN in enabling efficient CO₂ reduction, offering a pathway for further advancements in sustainable energy technologies.