Sluggish charge kinetics and low CO 2 affinity seriously limit the photocatalytic CO 2 reduction reaction. Herein, the simultaneous promotion of charge transfer and CO 2 activation over two-dimensional (2D) WO 3 nanosheets is achieved by coupling surface C-doping and oxygen vacancy. The surface-doped C atoms reconstruct the atomic surface of WO 3 by extracting oxygen lattice to generate the intimate oxygen vacancy (C−OV coordination) as the active center, which facilitates the CO 2 adsorption/activation, thus inducing the formation *CO 2 species. As a charge delivery channel, an exclusive W−O−C covalent bond formed by C−OV coordination could enhance the electron transfer. As a result, the as-designed catalyst exhibits 85.8% selectivity for CO 2 photoreduction to CO under the gas−solid phase reaction, with a yield rate of 23.2 μmol g −1 h −1 and a stable long-term reactivity over 24 h. Moreover, the in situ DRIFTS and DFT results reveal that this specific C−OV coordination enables the spontaneous CO 2 activation and proton-coupled electron transfer to guarantee the sustained formation of *COOH and, thus, smooth the photocatalytic CO 2 reduction reaction. This work develops a feasible strategy for electronic structure modification of photocatalysts with doping-induced oxygen vacancy to boost CO 2 activation and photoreduction.
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