A systematic study of [M(H(2)O)(n)(OH)(m)](q+) complexes of Te(IV) and Bi(III) in solution has been undertaken by means of quantum mechanical calculations. The results have been compared with previous information obtained for the same type of Po(IV) complexes ( J. Phys. Chem. B 2009 , 113 , 487 ) to get insight into the similarities and differences among them from a theoretical view. The evolution of the coordination number (n + m) with the degree of hydrolysis (m) for the stable species shows a systematic decrease regardless the ion. A general behavior on the M-O distances when passing from the gas phase to solution, represented by the polarizable continuum model (PCM), is also observed: R(M-O) values corresponding to water molecules decrease, while those of the hydroxyl groups slightly increase. The hydration numbers of aquaions are between 8 and 9 for the three cations, whereas hydrolyzed species behave differently for Te(IV) and Po(IV) than for Bi(III), which shows a stronger trend to dehydrate with the hydrolysis. On the basis of the semicontinuum solvation model, the hydration Gibbs energies are -800 (exptl -834 kcal/mol), -1580 and -1490 kcal/mol for Bi(III), Te(IV), and Po(IV), respectively. Wave function analysis of M-O and O-H bonds along the complexes has been carried out by means of quantum theory of atoms in molecule (QTAIM). Values of electron density and its Laplacian at bond critical points show different behaviors among the cations in aquaions. An interesting conclusion of the QTAIM analysis is that the prospection of the water O-H bond is more sensitive than the M-O bond to the ion interaction. A global comparison of cation properties in solution supplies a picture where the Po(IV) behavior is between those of Te(IV) and Bi(III), but closer to the first one.