The investigated tris(alkoxo) ligated POV6 ions [V V 6O13{(OCH2)3CR}2] 2-(Fig. Generally, negatively charged POMs in solution are surrounded by a dense shell of positively charged cations. On surfaces cations are also present, as they are deposited from solution together with bisligated POV6, enabling the formation of a stable structure of a single-POV6 complex. Our gas-phase DFT calculations model these situations and show that potassium, lithium, and magnesium cations are complexed to the positions of vanadium atoms (Fig. ), while ammonia and protons are attracted to oxygen atoms of the POV6 core. Further on, we will consider the fully optimized minimum energy configuration of the respective bisligated POV6-cation complexes.