Distinctive Cr-MOF@Da composites have been constructed using chromium-based metal-organic frameworks (MOFs) and diatomite (Da). The new materials have hierarchical pore structures containing micropores, mesopores and macropores. We have synthesized various morphologies of the MOF compound Cr-MIL-101 to combine with Da in a one-pot reaction step. These distinctive hierarchical pore networks within Cr-MIL-101@Da enable exceptional adsorptive performance for a range of molecules, including hydrogen (H₂), carbon dioxide (CO₂) and water (H₂O) vapor. Selectivity for H₂ or CO₂ can be moderated by the morphology and composition of the Cr-MIL-101 included in the Cr-MOF@Da composite. The encapsulation and growth of Cr-MIL-101 within and on Da have resulted in excellent water retention as well as high thermal and hydrolytic stability. In some cases, Cr-MIL-101@Da composite materials have demonstrated increased thermal stability compared with that of Cr-MIL-101; for example, decomposition temperatures >340 ℃ can be achieved. Furthermore, these Cr-MIL-101@Da composites retain structural and morphological integrity after 60 cycles of repeated hydration/dehydration, and after storage for more than one year. These characteristics are difficult to achieve with many MOF materials, and thus suggest that MOF–mineral composites show high potential for practical gas storage and water vapor capture.