To reduce the anthropogenic CO2 emissions produced from fossil fuel burning plants, the application of carbon capture and storage (CCS) is necessary and development of a more efficient and economically feasible CO2 capture process is essential as an alternative to the conventional amine scrubbing process which uses aqueous amine solutions. CO2 capture can be enhanced by improving both the gas−solid contact efficiency and by tuning a specific high-performance sorbent. The aim of this research is to investigate the adsorption of CO2 using impregnated mesoporous silica in a “confined-fluidized bed”. This non-conventional fluidized bed (sometimes also termed the “packed-fluidized bed”) seems suitable for improving the efficiency of gas−solid processes for which the bypass effect of the gas−solid contact caused by bubbling represents a major drawback. Results, expressed as grams of CO2 adsorbed per kilogram of material, are discussed in terms of amine load in the sorbent, breakthrough time and fraction of bed utilized. The stability of the materials after regeneration cycles is also discussed. The results obtained confirm that the confinement of the bed allows exploiting fluidization technology in adsorption operations. The operating velocity can be fixed at a value at which the thermal effects also connected to the operation are kept under control.