A general approach to promote IR light-driven CO2reduction within ultrathin Cu-based hydrotalcite-like hydroxy salts is presented. Associated band structures and optical properties of the Cu-based materials are first predicted by theory. Subsequently, Cu4(SO4)(OH)6nanosheets were synthesized and are found to undergo cascaded electron transfer processes based ond-dorbital transitions under infrared light irradiation. The obtained samples exhibit excellent activity for IR light-driven CO2reduction, with a production rate of 21.95 and 4.11 μmol g−1h−1for CO and CH4, respectively, surpassing most reported catalysts under the same reaction conditions. X-ray absorption spectroscopy and in situ Fourier-transform infrared spectroscopy are used to track the evolution of the catalytic sites and intermediates to understand the photocatalytic mechanism. Similar ultrathin catalysts are also investigated to explore the generality of the proposed electron transfer approach. Our findings illustrate that abundant transition metal complexes hold great promise for IR light-responsive photocatalysis.