Inverse sandwich clusters composed of a monocyclic boron ring and two capping transition metal atoms are interesting alloy cluster systems, yet their chemical bonding nature has not been sufficiently elucidated to date. We report herein on the theoretical prediction of a new example of boron-based inverse sandwich alloy clusters, V2B7−, through computational global-minimum structure searches and quantum chemical calculations. This alloy cluster has a heptatomic boron ring as well as a perpendicular V2dimer unit that penetrates through the ring. Chemical bonding analysis suggests that the inverse sandwich cluster is governed by globally delocalized 6π and 6σ frameworks, that is, double 6π/6σ aromaticity following the (4n+ 2) Hückel rule. The skeleton B−B σ bonding in the cluster is shown not to be strictly Lewis-type two-center two-electron (2c-2e) σ bonds. Rather, these are quasi-Lewis-type, roof-like 4c-2e V−B2−V σ bonds, which amount to seven in total and cover the whole surface of inverse sandwich in a truly three-dimensional manner. Theoretical evidence is revealed for a 2c-2e Lewis σ single bond within the V2dimer. Direct metal–metal bonding is scarce in inverse sandwich alloy clusters. The present inverse sandwich alloy cluster also offers a new type of electronic transmutation in physical chemistry, which helps establish an intriguing chemical analogy between inverse sandwich clusters and planar hypercoordinate molecular wheels.