The solar‐driven conversion of CO2 into carbon‐based fuels and other valuable chemical feedstocks is actively being pursued as an approach for curbing greenhouse gas emissions. Herein, a series of novel Fe‐based catalysts with different chemical compositions are successfully fabricated through the hydrogen reduction of MgFeAl‐layered double hydroxide nanosheets at temperatures from 300 to 700 °C. The catalysts obtained are denoted herein as Fe‐x, where x is the reduction temperature in celsius. Fe‐500 offers outstanding activity for the photothermal conversion of CO2 to C2+ hydrocarbons under ultraviolet‐visible (UV‐Vis) irradiation (CO2 conversion 50.1%, C2+ selectivity 52.9%). Characterization studies using X‐ray diffraction, extended X‐ray absorption fine structure, Mössbauer spectroscopy, and high‐resolution transmission electron microscopy determine that the Fe‐500 catalyst is comprised of Fe and FeOx nanoparticles on a MgO–Al2O3 mixed metal oxide support. Density functional theory calculations establish that heterostructures consisting of partially oxidized metallic Fe nanoparticles improve the CC coupling ability of CO2 hydrogenation intermediates, thus enhancing the selectivity to C2+ products. This work introduces a novel photothermal hydrogenation strategy for converting CO2 into valuable chemicals and also opens new avenues toward the development of related solar energy utilization schemes. A series of Fe‐containing catalysts (denoted herein as Fe‐x) are successfully synthesized by partial H2 reduction of a MgFeAl‐layered double hydroxide nanosheet precursor at different temperatures (x) in the range 300–700 °C. The Fe‐500 catalyst, comprised of Fe0/FeOx nanoparticles on a MgO‐Al2O3 support, displays outstanding photothermal performance for CO2 hydrogenation to C2+ hydrocarbons under ultraviolet‐visible (UV‐Vis) irradiation.