We developed a new route for synthesis of Cr-based porous coordination polymers (PCPs) with azole ligands and characterized the unique open structures by single-crystal X-ray studies and other spectroscopy techniques. Chromium-based PCPs have been prepared from azolate ligands 3,5-dimethyl-1H-pyrazole-4-carboxylic acid (H2dmcpz) and 1,4-di(1H-tetrazole-5yl)benzene (H2BDT) by solvothermal reactions under an Ar atmosphere. [Cr3O(Hdmcpz)6(DMF)3]⊃DMF (1⊃DMF) is a coordination compound that forms a hydrogen-bonded porous network. [Cr3O(HBDT)2(BDT)Cl3)]⊃DMF (2⊃DMF) possesses a new type of trinuclear chromium μ3-O unit cluster and the novel topology of a Cr-based PCP with 700 m(2) g(-1) of Brunauer-Emmett-Teller surface area. [Cr(BDT)(DEF)]⊃DEF (3⊃DEF) is structurally flexible and reactive to O2 molecules because of the unsaturated Cr(2+) centers. This is the first report of a Cr-based PCP/metal-organic framework with noncarboxylate ligands and characterization by single-crystal X-ray diffraction.