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.