The solvation behavior of various silver(I) salts, viz. silver (I) iodate, bromate and sulfate in iso-dielectric solvent mixtures of methanol and N-methyl-2-pyrrolidinone (NMP) has been investigated using Gibbs transfer energies and solvent transport number measurements. The Gibbs transfer energies of the salts were split into their individual ionic contributions using both negligible liquid junction potential method (nLJP) and the reference electrolyte method using tetraphenylarsonium tetraphenylborate (TATB). The results show a significant heteroselective solvation of all salts beyond XNMP = 0.5 with silver ion being selectively solvated by NMP and the an-ions by methanol. © VCH Verlassgesellschaft mbH, 1997.