Three new isomorphic porous MOFs with the molecular formula of RE2(phen)(2)(fdc)(3)center dot 2(H2O) have been hydrothermally synthesized. The structure, topology, compositions and thermal stability were studied in detail. They show unique H2O and H2S adsorption, CO2 selective separation from mixed CH4 and C2H6 gases, and interesting photoluminescence in both bulk powder and a single crystal particle, in particular, the luminescence of bulk powder form changes upon dehydration which may be found applications as multifunctional materials.