[en] The reaction of ligand substitution with solvent molecules in a complex of electron-excited ions of Eu³⁺(⁵D₀) and Sm³⁺(sup(4)Gsub(5/2)) with an anion of 1-naphthalic acid has been studied by the luminescent kinetic spectroscopy. The dissociation rate of monoligand inner spherical complex of an excited Eu³⁺(⁵D₀) has been determined in methanol (d₄(2.5x10³c^-1)) and in a mixed methanol-water solvent at a different water content. For the complex of excited Sm³⁺ (sup(4)Gsub(5/2)) the rate of the similar process has been measured in mixtures of methanol-water, and in pure D₂O (4.4x10⁶c^-1) and H₂O(5.5x10⁶c^-1) at 295 K. It is shown that outside anions produce an essential influence on the rate of ligand substitution in methanol. The mechanisms of the above processes are discussed