AbstractArtificial photosynthesis, light-driving CO₂ conversion into hydrocarbon fuels, is a promising strategy to synchronously overcome global warming and energy-supply issues. The quaternary AgInP₂S₆ atomic layer with the thickness of ~ 0.70 nm were successfully synthesized through facile ultrasonic exfoliation of the corresponding bulk crystal. The sulfur defect engineering on this atomic layer through a H₂O₂ etching treatment can excitingly change the CO₂ photoreduction reaction pathway to steer dominant generation of ethene with the yield-based selectivity reaching ~73% and the electron-based selectivity as high as ~89%. Both DFT calculation and in-situ FTIR spectra demonstrate that as the introduction of S vacancies in AgInP₂S₆ causes the charge accumulation on the Ag atoms near the S vacancies, the exposed Ag sites can thus effectively capture the forming *CO molecules. It makes the catalyst surface enrich with key reaction intermediates to lower the C-C binding coupling barrier, which facilitates the production of ethene.