A three-dimensional, highly porous metal-organic framework [Zn4O(bdc)(bpz)(2)]center dot 4DMF-6H(2)O (1) (bdc = 1,4-benzenedicarboxylate, bpz = 3,3',5,5'-tetramethyl-4,4'-bipyrazolate) constructed by Zn4O clusters with bdc and bpz linkers, has been prepared and structurally characterized. The N-2 sorption measurements reveal that 1 exhibits high porosity with a Langmuir surface area of 1908 m(2)/g and a pore volume of 0.58 cm(3)/g. Compound 1 features hydrophobic channels with a free passage of similar to 8.2 angstrom defined by the methyl groups from bpz, and it exhibits nice sorption capability for benzene and toluene and interesting two-step sorption behavior for methanol. Meanwhile, 1 also exhibits interesting guest-dependent luminescent properties.