The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}(2)(V2O28)]center dot 10H2O (1, cyclam = 1,4,8,11-tetraazacyclotetradecane) was prepared by reaction of (VO3)(-) anions and {Cu(cyclam)}(2+) complexes in NaCl (aq) at pH 4.6-4.7 and characterized by elemental analyses, thermogravimetry, and X-ray diffraction (powder, single-crystal) techniques. Compound 1 exhibits a POMOF-like supramolecular open-framework built of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross sections of 10.4 X 8.8 angstrom(2). The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase la. This permanent microporosity renders interesting functionality to 1, such adsorption of CO2 over N-2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly stable, tricyclic alkane adamantane.