Crystalline porous hybrid materials with metal-organic frameworks (MOFs) are currently of great interest and importance due to their novel coordination structure, relatively facile preparation, special properties and potential practical applications. In this talk, synthesis of porous hybrid solids and their adsorption and catalytic properties will be presented. We have first demonstrated that microwave method provides a challengeable opportunity to effectively synthesize porous hybrid materials such as MIL-77 and MIL-101. The cubic metal carboxylate, MIL-101 with giant pores and very large surface areas has been synthesized efficiently and quickly under microwave irradiation, leading to very small dimensions with nanometer size especially for short crystallization time. This material exhibited the huge and fast adsorption of benzene, making it a good candidate for sorptive removal of harmful organic contaminants. The presence of CUS chromium(III) sites in chromium(III) terephthalate MIL-101 with zeotypic giant pores has also found to provide an intrinsic chelating property with electron-rich functional groups. Moreover, site selective catalysis with surface-functionalized mesoporous MOFs has been also proposed. Theporous MIL-100 with iron species showed good catalytic activity and selectivity for Friedel-Carafts benzylationof benzene with benzyl chloride. We have also succeeded in the synthesis of a new coordination solid of Co(II)-pyridine-2,4-dicarboxylate (CUK-1) crystallizees into the monoclinic space group C2/c. It has 1-dimensional diamond-shaped channels that traverse the structure and contain guest water molecules of crystallization. The gas-selective sorption properties ofCUK-1 have shown that the material has unprecedented selectivity for O2over similar small molecule substrates, in addition to high selectivity of CO2 over CH4, suggesting that CUK-1 behaves as a size-selective molecular sieve. We have also explored successful application of CUK-1 to gas chromatographic separation of light gases.