To make these POV6 nanoswitches suitable for applications at the level of single molecules incorporated in support structures, the challenge of the underlying charge stabilization needs to be addressed and thoroughly understood. Specifically, the ability of bisligated POV6 complexes to take up electrons while preserving the geometry, without leaking the charge to ligands or the environment, and the role of countercations, ligands, and/or the support materials in this leakage need to be explored. Herein, we examine theoretically the maximum possible charge loading of the Lindqvist-type polyoxovanadate [V V 6O13{(OCH2)3CR}2] 2-with three different R groups, and in the presence of model NH4 + , Li + , K + , H + , and Mg 2+ counterions. The choice of the R group is based on the ability of R to undergo further derivatization, allowing to chemically engineer more complex systems, e.g. via azide-alkyne cycloaddition. We show that the ideal setup does not depend on the type of the ligand R group, while the best electron capacity of up to 9 electrons can be achieved when applying hydrogen ions as charge-balancing entities for the bisligated POV6 core. Two types of calculations have been carried out. In the first type, sequential addition of electrons to the neutral systems (NH4 + )2-[V V 6O13{(OCH2)3CR}2] 2-and (Mg 2+ )-[V V 6O13{(OCH2)3CR}2] 2-is performed. Thus, the total charge of each model system increases to polyanionic states. In the second type, the same process takes place, but the charge of additional electrons is compensated by the addition of counterions (H + , NH4 + , K + , Li + , Mg 2+ ), so that the total system remains charge neutral. We will show that charge-compensated POV6 cores can take up at least 4 additional electrons, and even up to 9 for the case of proton counterions.