Photocatalytic CO2 conversion into valuable solar fuels is highly appealing, but lack of directional charge-transfer channel and insufficient active sites resulted in limited CO2 reduction efficiency and selectivity for most photocatalytic systems. Herein, we designed and fabricated rare-earth La single-atoms on carbon nitride with La–N charge-transfer bridge as the active center for photocatalytic CO2 reaction. The formation of La single-atoms was certified by spherical aberration-corrected HAADF-STEM, STEM-EELS, EXAFS, and theoretical calculations. The electronic structure of the La–N bridge enables a high CO-yielding rate of 92 μmol·g–1·h–1 and CO selectivity of 80.3%, which is superior to most g-C3N4-based photocatalytic CO2 reductions. The CO production rate remained nearly constant under light irradiation for five cycles of 20 h, indicating its stability. The closely combined experimental and DFT calculations clearly elucidated that the variety of electronic states induced by 4f and 5d orbitals of the La single atom and the p–d orbital hybridization of La–N atoms enabled the formation of charge-transfer channel. The La–N charge bridges are found to function as the key active center for CO2 activation, rapid COOH* formation, and CO desorption. The present work would provide a mechanistic understanding into the utilization of rare-earth single-atoms in photocatalysis for solar energy conversion.

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The alternative charge arrangement on the {010} facet of BiOCl facilitates benzyl oxidation and selectivity for benzoic acid ring-opening reactions, subsequently resulting in remarkably enhanced photocatalytic efficiency.

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