This work reports the Calcium-Looping (CaL) multicycle performance under energy storage and CO2 capture conditions of different Al-composites prepared by milling mixtures of nanoalumina and natural limestone powders. The micro-and nanostructure of the composites have been analyzed by X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy as affected by the type of CaL conditions employed, either for energy storage in Concentrated Solar Power (CSP) plants or for post-combustion CO2 capture. Two types of calcium aluminates are formed under these diverse CaL conditions. A calcium aluminate with ratio Ca/Al < 1 (Ca4Al6O13) is formed under CaL-CSP conditions, which helps stabilize the CaO microstructure and mitigate pore-plugging. On the other hand, a crystalline phase Ca3Al2O6 is formed (Ca/Al > 1) under CaL-CO2 capture conditions presumably due to the higher calcination temperature, which withdraws from the sorbent a relatively higher amount of active Ca. Moreover, the addition of nano-alumina, and the consequent generation of calcium aluminate, affects in a diverse way the microstructure and morphology of the CaO particles as depending on the CaL application, which critically modifies the performance of the composites.