Aqueous solutions of the polyoxometallate α-PW12O403− Keggin anion “PW3−” have been simulated by molecular dynamics, comparing two anion concentrations (0.06 and ca. 0.15 mol l−1) and Cs+, NBu4+, UO22+, Eu3+, H3O+ and H5O2+ as neutralizing Mn+ counterions. They reveal marked counterion effects of the degree of salt dilution, cation–anion and anion–anion relationships. The hydrophobic NBu4+ cations tend to surround PW3−’s via loose contacts, leading to “phase separation” between water and a humid salty domain, overall neutral, where all ions are concentrated. The other studied cations are more hydrophilic and generally separated from the PW3− anions. The most important finding concerns the aggregation of PW’s, mostly as dimers with short contacts (P⋯P < 12 Å), but also as higher (PW3−)n oligomers (n = 3 to 5) in concentrated solutions where the proportion of the aggregates ranges from ca. 9 to 46%, depending on the counterion. While Eu3+ and UO22+ are fully hydrated and interact at short distances with PWs as solvent-separated ion pairs, Cs+ can form contact ion pairs, as well as solvent-separated ions. Among the mono-charged counterions, H5O2+ gives highest aggregation (ca. 47%, involving 32% of dimers, 11% of trimers and 3% of tetramers), pointing to the influence of the proton state (H5O2+vs. H3O+) on PW’s aggregation and condensation. The dynamic properties are also dependent on Mn+: the PW’s diffusion coefficients are lowest with NBu4+, and highest for Cs+, thus reflecting the degree of ion condensation in water. The role of water on the solution state of the PW salts is further demonstrated by simulating the most concentrated systems in methanol solution. Because MeOH solvates less well the Mn+ cation than does H2O and cannot afford bridging relays between PW’s, one finds a higher proportion of PW3−⋯Mn+ contacts, and no (PW3−)n oligomers with short contacts in methanol.