Mg-Al mixed metal oxides (MMOs), derived from the decomposition of layered double hydroxides (LDHs), have been purposed as a material for CO2 capture of industrial plant emissions. In order to aid in the design and optimization of these materials for CO2 capture at 200 °C, we have used the combination of solid-state nuclear magnetic resonance (ssNMR) and density functional theory (DFT) to characterize the CO2 gas sorption products and determine the various sorption sites in the Mg-Al MMOs. Comparison of DFT cluster calculations with 13C chemical shift of the chemisorbed products indicates that mono and bi-dentate carbonate are formed at the Mg-O site with an adjacent Al substitution of an Mg atom, while bicarbonate is formed at Mg-OH sites without adjacent Al substitution. Quantitative 13C NMR shows an increase in the relative amount of strongly basic sites, where the monodentate carbonate product is formed, with increasing Al mole % in the MMO. This detailed understanding of the various basic Mg-O sites presents in the MMO material, and the formation of the carbonate, bidentate carbonate and bicarbonate chemisorbed species yields new insight into the mechanism of CO2 adsorption at 200 °C which can further aid in the design and capture capacity optimization of the materials.