The KU-2 and KU-1 universal cationites were found to exhibit partly selective properties with respect to Gd3+ ions. As distinct from the transition group cations studied earlier, gadolinium ions formed centers with SO 3 − functional groups even in sulfo resin matrices hydrated to the greatest extent, and the fraction of these complexes increased as free water was removed from ionite matrices. The EPR spectra of gadolinium aquacomplexes in hydrated polymers were similar to their spectra in aqueous solutions. The strong crystal field condition (D hv) with the presence of axial and rhombic components was fulfilled for fixed complexes. The spectra corresponded to complexes of two types. The effective g-factors and λ = E/D parameters were calculated to describe the spectra of systems with spin S = 7/2 quantitatively. The correlation times of rotational motion of aquacomplexes in hydrated cationites were determined. These times were found to be longer (1.5 to 3 times) than in aqueous solutions. Dipole-dipole interactions between gadolinium ions were studied to estimate the local concentrations of sorbed ions in large-sized pores.