Interfacial modulation promoted CC coupling in selective methane oxidation to ethanol

Selective methane oxidation to ethanol remained a formidable challenge. Herein, MOF‐derived In 2 O 3 was synthesized via MIL‐68(In) pyrolysis. The optimized In 2 O 3 ‐500 achieved an ethanol yield of 10.8 mmol·g −1 ·h −1 under full‐spectrum illumination. These performances were attributed to carboxylate type CO related interfacial modulation, which enriched surface electron density and promoted CC coupling. During derivation, precursor derived carbon species were retained as carboxylate type CO related structures and interacted with the InO framework, inducing surface charge redistribution. Compared with In 2 O 3 ‐400, which retained residual MOF structures, and highly crystalline In 2 O 3 ‐600, which exhibited severe charge recombination, In 2 O 3 ‐500 exhibited a higher surface electron density and enhanced ·OH and ·CH 3 generation, thereby promoting the stepwise oxidation of *CH 3 to *CH 3 O and *CH 2 O. The enriched *CH 2 O and *CH 3 intermediates further facilitated C–C coupling to form ethanol. These findings highlighted the role of electron‐rich surfaces in steering methane conversion toward ethanol.