A general approach to promote IR light-driven CO₂ reduction 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)₆ nanosheets were synthesized and are found to undergo cascaded electron transfer processes based on d-d orbital transitions under infrared light irradiation. The obtained samples exhibit excellent activity for IR light-driven CO₂ reduction, with a production rate of 21.95 and 4.11 μmol g⁻¹ h⁻¹ for 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.