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Light‐driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air‐promoted strategy is explored for efficient and durable light‐driven hydrogen production from ethanol over a core/shell Cr2O3@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the Cr2O3@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H2 evolution by photogenerated electrons. Afterward, O2 can be evolved into active oxygen species and promote the deprotonation and C−C cleavage of the key C2 intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9 mole H2 per gram Cr2O3@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000 mole H2 per mole Cr2O3 over a long‐term operation of 180 hours. Notably, an unprecedented light‐to‐hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising. [ABSTRACT FROM AUTHOR]