The selective solvation behavior of copper(II) iodate, formate, and benzoate in the isodielectric solvent mixtures of methanol and N-methyl-2-pyrrolidinone has been studied using the standard Gibbs transfer energies and solvent transport number measurements. The standard Gibbs transfer energies of various ions were determined on the basis of the tetraphenylarsonium tetraphenylborate (TATB) assumption. The results were interpreted in terms of heteroselective solvation of all the salts with copper(II) ion being selectively solvated by N-methyl-2-pyrrolidinone and anions by methanol.