We investigated the ability of the polyoxovanadate complexes (Cat)n[V V 6O13{(OCH2)3CR}2] with three types of organic ligands R and various countercations Cat to take up external electrons. The results show that the possible uptake of electrons without charge leakage from the central POV6 core depends on the type of Cat that is used for charge compensation. The bisligated POV6, charged balanced by monovalent alkali cations, can accommodate four additional electrons, whereas protons as countercations remain stable even up to the addition of nine electrons. For the reported stable electronic states, no effect of the R group on charge leakage is observed, which is different from the case when R bears a metalorganic moiety in such Lindqvist-type hexavanadates. Importantly, the structural integrity of the studied POV6 core is preserved during electron uptake. Our calculations indicate that the highly stable configurations of POV6 with four to nine additional electrons offers opportunities in the fields of multi-bit data storage and batteries. Countercations in the vicinity of the tris(alkoxo) ligated POV6 core play a significant role as controllers of charge leakage to ligands and environment in electron transport across the [V V 6O13{(OCH2)3CR}2] 2-structure.