The binding of Y(III) ions to surface-immobilized single-stranded 20-mers of guanine was studied using the Eisenthal chi((3)) technique and AFM. The free energy of binding for Y(:11) to the G(20) sequence was found to be -39.5(8) kJ/mol. Furthermore, yttrium binds much more strongly to surface-immobilized oligonucleotides than the divalent metals previously reported. At maximum surface coverage, Y(III) ion densities range between one to three ions bound per strand. Comparatively, Mg(II) binds to the G(20)-functionalized interface in much higher ion densities. This result may be explained, in part, by the larger hydration sphere radius of Y(III) compared to that of Mg(II). The ion loading and binding free energy results, in conjunction with other surface and bulk aqueous phase studies, suggest that a fully hydrated +2 or +3 yttrium ion binds to the oligonucleotides through an outer-sphere mechanism. Tapping mode AFM results indicate that oligonucleotide height does not appreciably decrease following Y(III) binding. These results, together with the low ion densities for Y(III) ions, indicate that Y(III) strand loading may not significantly decrease the intrastrand Coulombic repulsions in order to cause a significant decrease in oligomer height.