The deposition of Mo on gamma-alumina by the equilibrium adsorption method starting from ammonium heptamolybdate has been studied. Spectroscopic results converge to indicate that a previously unrecognized species, i.e., the Anderson-type heteropolymolybdate [Al(OH)(6)Mo6O18](3-), plays a major role in this type of synthesis as it is quantitatively formed in the solution within a few hours, by reaction of the heptamolybdate with dissolved aluminic species. This results in a considerable increase of alumina solubility in conditions generally thought to be nonaggressive. Furthermore, this species is also present in the solid catalyst after deposition, although it is harder to observe than in the liquid phase. A parallel is drawn with a well-known idea from the field of geochemistry, i.e., ligand-promoted oxide dissolution. The relevance of this phenomenon in catalyst preparation is evaluated in realistic conditions corresponding to published studies and/or industrial procedures. It is concluded that strong metal-support interaction in the deposition stage by surface dissolution followed by reaction in the liquid phase is most likely to be an important phenomenon, not only for cationic metal precursors as previously known but also for anionic precursors such as molybdates.