The development of highly efficient CaO-based pellet sorbents, using inexpensive raw materials (limestones) or the spent sorbent from CO2 capture cycles, and commercially available calcium aluminate cements (CA-14, CA-25, Secar 51, and Secar 80), is described here. The pellets were prepared using untreated powdered limestones or their corresponding hydrated limes and were tested for their CO2 capture carrying capacities for 30 carbonation/calcination cycles in a thermogravimetric analyzer (TGA). Their morphology was also investigated by scanning electron microscopy (SEM) and their compositions before and after carbonation/calcination cycleswere determined by X-ray diffraction (XRD). Pellets prepared in this manner showed superior behavior during CO2 capture cycles compared to natural sorbents, with the highest conversions being > 50% after 30 cycles. This improved performance was attributed to the resulting substructure of the sorbent particles, i.e., a porous structure with nanoparticles incorporated. During carbonation/calcination cycles mayenite (Ca12Al14O33) was formed, which is believed to be responsible for the favorable performance of synthetic CaO-based sorbents doped with alumina compounds. An added advantage of the pellets produced here is their superior strength, offering the possibility of using them in fluidized bed combustion (FBC) systems with minimal sorbent loss due to attrition.