Dual Active Sites with Charge‐asymmetry in Organic Semiconductors Promoting C‐C Coupling for Highly Efficient CO2 Photoreduction to Ethanol

Selective CO2 photoreduction into high‐energy‐density and high‐value‐added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C‐C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon‐based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon‐based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as‐formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97% for C2H5OH and C2H5OH yield of 0.80 mmol g‐1 h‐1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non‐metal multi‐site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.