Using a combination of thermogravimetric and sorption/desorption experiments along with theoretical calculations, this study presents a comprehensive investigation of the CO oxidation-capture mechanism catalyzed by lithium manganate (Li 2 MnO 3 ). Experimental results demonstrate efficient CO oxidation-capture by Li 2 MnO 3 across a broad temperature range. However, the introduction of CO 2 into the reaction flow induces significant changes in the CO oxidation-capture process. Specifically, CO 2 alters the sorption−desorption equilibrium toward carbonate formation, leading to decreased CO capture efficiency and increased CO 2 partial pressure owing to elevated activation energy. Theoretical calculations based on a cluster model explain the experimental observations of the primary CO oxidation pathway on the Li 2 MnO 3 surface. This pathway involves the formation of intermediates for CO capture, CO 2 generation, and subsequent release, leading to activation of the surface from Li 2 MnO 3 to Li 2 MnO 3−δ . This process resulted in the reduction of Mn 4+ to Mn 3+ and Mn 2+ . The competitive processes for CO 2 and CO capture explain the inhibition of CO sorption. Additionally, carbonate moieties form on the ceramic surface, with Gibbs-free activation energies corresponding to the experimental values for the CO oxidation-capture process. Calculations revealed stability differences between CO and CO 2 intermediates for Li 2 MnO 3 and Li 2 MnO 3−δ , which agreed with the experimental observations. To validate this theoretical model, a second comparable system was analyzed. Experimental reports have demonstrated that lithium zirconate (Li 2 ZrO 3 ) captures CO 2 , unlike Li 2 MnO 3 . Computational analysis supports this, showing that the interaction between the highest occupied molecular orbital (HOMO) of CO 2 and lowest unoccupied molecular orbital (LUMO) of the Zr atom enables CO 2 capture by lithium zirconate, in contrast to that determined for Mn in lithium manganate. This disparity in reactivity elucidates the differing responses of Li 2 MnO 3 and Li 2 ZrO 3 toward CO and CO 2 . The correspondence between these insights and experimental data highlights the indispensable role of computational models in clarifying the reaction mechanisms and providing theoretical explanations for chemically significant processes.