The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·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 × 8.8 Å2. 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 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane. ; This work was funded by Eusko Jaurlaritza/Gobierno Vasco (Grant No. IT477-10), MINECO (Grant No. MAT2013-48366-C2-2-P), and UPV/EHU (Grant No. UFI11/53). J.A.-M. thanks Generalitat Valenciana and FEDER (Grant No. PROMETEO2/2014/010), as well as MICINN and Plan E (Grant No. CTQ2012-31762) for financial support.