A teetotum form is found as the global equilibrium structure of V2B7+/0/- clusters. Formation of a bimetallic configuration and aromaticity are found to be dominant factors stabilizing the doped V2B7+/0/- teetotum structures. Magnetic ring current maps indicate the V2B7+ cation as doubly aromatic. Exploration on the interactions of one and two CO2 molecules with the pure B-7(-) and doped VB7 and V2B7+/0/- clusters shows that these boron-based clusters can capture CO2 and transform it through a dissociative adsorption mechanism. The pure B-7(-) anion cluster performs even better than the doped clusters in CO2 capture ability.