Hexalithium cobaltate (Li6CoO4) was synthesized by a solidstate reaction and evaluated as a possible simultaneous CO oxidant and CO2 chemisorbent, namely, as a bifunctional material. The analysis of this process was performed using catalytic and thermogravimetric techniques, under dynamic and isothermal conditions in both cases. After this, the isothermal sample products were characterized by X-ray diffraction (XRD) and Raman spectroscopy. Catalytic and thermogravimetric experiments were performed in the presence and absence of oxygen to further analyze the reaction paths performed during the double CO oxidation and chemisorption process. The thermogravimetric analysis evidenced the carbonation process through lithium carbonate formation, while catalytic results clearly showed that Li6CoO4 was able to perform the CO oxidation even if the CO2 produced was not completely chemically trapped. Moreover, different compounds were identified on the isothermal sample products (determined by XRD) depending on the oxygen provision, indicating variations in the reaction paths. Since lithium cobaltate (LiCoO2) was obtained as an isothermal product during the experiments in the presence of oxygen, it was synthesized and analyzed as a possible catalyst and sorbent bifunctional material. LiCoO2 showed a high catalytic behavior toward CO oxidation, although its CO2 chemisorption capacity was not as high as expected, at least under the same physicochemical conditions used for Li6CoO4. Based on these results, it can be established that Li6CoO4 produces LiCoO2 as a secondary phase during the CO oxidation and carbonation process. Thus, the real CO2 capture on Li6CoO4 can be established as 5/6 of the lithium content of the ceramic.