AbstractThe directional transformation of carbon dioxide (CO₂) with renewable hydrogen into specific carbon-heavy products (C₆₊) of high value presents a sustainable route for net-zero chemical manufacture. However, it is still challenging to simultaneously achieve high activity and selectivity due to the unbalanced CO₂ hydrogenation and C–C coupling rates on complementary active sites in a bifunctional catalyst, thus causing unexpected secondary reaction. Here we report LaFeO₃ perovskite-mediated directional tandem conversion of CO₂ towards heavy aromatics with high CO₂ conversion (> 60%), exceptional aromatics selectivity among hydrocarbons (> 85%), and no obvious deactivation for 1000 hours. This is enabled by disentangling the CO₂ hydrogenation domain from the C-C coupling domain in the tandem system for Iron-based catalyst. Unlike other active Fe oxides showing wide hydrocarbon product distribution due to carbide formation, LaFeO₃ by design is endowed with superior resistance to carburization, therefore inhibiting uncontrolled C–C coupling on oxide and isolating aromatics formation in the zeolite. In-situ spectroscopic evidence and theoretical calculations reveal an oxygenate-rich surface chemistry of LaFeO₃, that easily escape from the oxide surface for further precise C–C coupling inside zeolites, thus steering CO₂-HCOOH/H₂CO-Aromatics reaction pathway to enable a high yield of aromatics.