Understanding the aqueous state of discrete metal-oxo clusters, prenucleation clusters, and even simple ions is valuable for controlling the growth of metal-oxide materials from water. Niobium polyoxometalates (Nb-POMs) are unique in the aqueous metal-oxo cluster landscape in their unusual solubility behavior: specifically, their solubility in water increases with increasing ion-pairing contact with their counterions, and thus provides a rare opportunity to observe these and related solution phenomena. Here, we isolate in the solid state the monomeric and dimeric building blocks, capped Keggin ions, of the extended Keggin chain materials that are now well-known: not only in Nb-POM chemistry, but Mo and V POM chemistry as well. Rb-13[GeNb13O41]center dot 23H(2)O (Rb 1), Cs-10.6[H2.4GeNb13O41]center dot 27H(2)O (Cs1) and Cs18H6[(NbOH)-SiNb12O40](2)center dot 38H(2)O (Cs2) were characterized by single-crystal X-ray diffraction. Small angle X-ray scattering (SAXS) of solutions of Rb1 and Cs1 in varying conditions revealed oligomerization of the monomers into chain structures: the extent of oligomerization is controlled by pH, concentration, and the counterion. We distinctly observe chains of up to six Keggin ions in solution, with the large alkali cations for charge-balance. This combined solid state and solution study reveals in great detail the growth of a complex material from discrete monomeric building blocks. The fundamentals of the processes we are able to directly observe in this study, ion-association and hydrolysis leading to condensation, universally control the self-assembly and precipitation of materials from water.