The synthesis of an NbO-type metal-organic framework was achieved by design: o-Br-BDC (BDC = benzenedicarboxylate) was used to direct the formation of Cu2(CO2)4 paddle wheel units at 90° to each other and thus yield the target network. The compound was formulated as Cu2[o-Br-BDC]2(H2O)2·(DMF)8(H2O)2 (MOF-101) and characterized by single-crystal X-ray diffraction [cubic, space group lm3m (No. 229) with a = 21.607(3) Å, V = 10088(2) Å3, Z = 6], which fully confirmed the presence of the expected structure. Despite having very large apertures and voids, MOF-101 has a noninterpenetrated structure, an intriguing observation that is discussed in the context of dual structures.