In the last two decades different lithium and sodium ceramics have been proposed as potential high temperature CO2 captors, under different physicochemical conditions. Moreover, in the last five years, it has been evidenced that some of these alkaline ceramics can be used as possible bifunctional materials for CO2 capture and subsequent catalytic conversion to added value products. This kind of alkaline ceramics have been tested in different catalytic reactions (where CO2 has been previously chemically trapped) such as methane reforming and water gas shift processes. These processes (capture reactions and the subsequent methane reforming process) are environmentally important, as CO2, CO and CH4 are catalytically converted into an added value product, the syngas. Moreover, it has been evidenced that the same alkaline ceramics can be used for CO oxidation-capture process, which would be highly useful in hydrogen enrichment process. Therefore, the aim of this presentation is to show the most recent advances obtained about the next three different aspects: 1) CO2 capture on alkaline ceramics; 2) the use of these ceramics as bifunctional materials for the CO oxidation-capture process; and 3) The methane reforming reaction for the syngas production, using the CO2 chemically trapped in the alkaline ceramics.