As massive amounts of carbon dioxide (CO2) have been emitted into the atmosphere causing severe global warming problems, developing carbon-negative techniques to control atmospheric CO2concentrations is enormously urgent. Herein, by coupling the direct atmosphere CO2capture adsorbent ZSM-5 with the CO2reduction photocatalyst NiV2Se4, we present the first synergistic approach for concentrating and converting atmospheric CO2into C2solar fuels. A C2H6yield of 1.85 μmol g–1h–1has been achieved in the air, outperforming state-of-the-art direct atmospheric CO2conversion photocatalysts. Comprehensive characterizations show that ZSM-5 enhances CO2capture from the atmosphere, improving the interfacial interaction of CO2on the NiV2Se4surface for C–C coupling of CH3* to form C2H6. This work demonstrates the first example of integrating direct CO2capture material with a CO2reduction photocatalyst for atmospheric CO2capture and utilization, which paves the way for the negative-carbon technology development under worldwide carbon-neutral pressure.