The mechanism of the deposition of the W-(vi) species from aqueous solutions on the gamma-alumina surface is refined in this work by investigating critical mechanistic points. A methodology recently developed to investigate the deposition of the Co-(II), Ni-(II), Cr-(VI), and Mo-(VI) on gamma-alumina has been applied. This methodology is based on the "2pK/one site" and "triple-layer" models and involves the writing down of various deposition equilibria, the derivation of the corresponding equations, the calculation of the amount of the deposited W-(vi) (through the calculated concentrations of the W-(vi) species formed on gamma-alumina) at various values of the impregnating parameters, the calculation of the variation, with pH, of the zeta-potential and of the difference in the H+ ions consumption by the support surface in the presence and absence of the W-(vi) species in the impregnating solution. The comparison of the calculated values of the aforementioned parameters with the corresponding ones achieved from deposition experiments, potentiometric titrations, and microelectrophoresis allowed us to establish the mechanism of deposition of W-(vi) species on gamma-alumina. It was found that although eight different W-(vi) species are present in the impregnating solution under the conditions of deposition, the mechanism. According to this mechanism only two W-(vi) species contribute to the whole deposition.