TiO2 nanotubes constitute very promising nanomaterials for water decontamination by the removal of cations. We combined a range of experimental techniques from structural analyses to measurements of the properties of aqueous suspensions of nanotubes, with (i) continuous solvent modeling and (ii) quantum DFT-based simulations to assess the adsorption of Cs+ on TiO2 nanotubes and to predict the separation of metal ions. The methodology is set to be operable under realistic conditions, which, in this case, include the presence of CO2 that needs to be treated as a substantial contaminant, both in experiments and in models. The mesoscopic model, based on the Poisson–Boltzmann equation and surface adsorption equilibrium, predicts that H+ ions are the charge-determining species, while Cs+ ions are in the diffuse layer of the outer surface with a significant contribution only at high concentrations and high pH. The effect of the size of nanotubes in terms of the polydispersity and the distribution of the inner and outer radii is shown to be a third-order effect that is very small when the nanotube layer is not very thick (ranging from 1 to 2 nm). Besides, DFT-based molecular dynamics simulations demonstrate that, for protonation, the one-site and successive association assumption is correct, while, for Cs+ adsorption, the size of the cation is important and the adsorption sites should be carefully defined.