The development of porous metal-organic frameworks that can retain structural integrity under harsh physical and chemical conditions is essential from the perspective of their use in adsorption, catalysis, and sensors. Herein, a lanthanum carboxylate framework was found to exhibit exceptional stability, not only robust in boiling aqueous solutions at pH 2-12 and in boiling common organic solvents over 24 h but also stable upon ball milling for 1 h. Furthermore, this framework displayed highly selective separation for CO2 over N2 ( Sads = 940), as well as size-dependent selective adsorption behavior of water and alcohols.