​Ordered mesoporous silica-NH₂-MIL-53(Al) core–shell spheres of about 4 μm in diameter have been synthesized by seeding the corresponding mesoporous silica spheres (MSSs) with crystals of NH₂-MIL-53(Al) and subsequent secondary crystal growth into a MOF shell. The morphology of the particles was analyzed by SEM, while TGA, EDX and XRD characterizations gave information on the composition and structure of this material and the activation of the MOF. N₂ adsorption analysis revealed that the NH₂-MIL-53(Al) shell controlled the access of guest molecules into the hydrophilic silica mesoporous structure, while the breathing behavior of the microporous NH₂-MIL-53(Al) shell was confirmed by CO₂ adsorption isotherms.