Nuclear facilities generate contaminated effluents containing radionuclides (such as Cs, Sr, Co…) that need to be removed for human health and environment protection reasons. Inorganic sorbents are attractive candidate materials because of their high thermochemical and radiation stability. Furthermore, their microstructural and surface properties can be adjusted to increase the radionuclide extraction efficiency. In this study, nanostructured sorbents consisting of aggregated TiO2 nanocrystals with different surface properties and microstructures were prepared in supercritical CO2 by varying the synthesis temperature. The Sr2+ sorption process was characterized by measuring the surface properties and extraction capacity of the samples as a function of pH. In basic effluents, the Sr sorption capacity of these materials is directly linked to their specific surface area and sorption site density through a classic physisorption mechanism. Sr2+ diffusion into the mesopores leads to rapid initial sorption, which is followed by a slower process driven by a proposed multistep mechanism. This mechanism involves the initial adsorption of partially hydrated Sr2+ ions up to complete TiO2 surface coverage, which implies slower Sr ion diffusion due to steric hindrance in small mesopores thus limiting access to additional secondary sites with lower adsorption energies.