The solvation behaviour of the salts, silver bromate, silver acetate and silver sulphate has been investigated in the binary mixtures of N,N-dimethyl formamide (dmf) and water. The Gibbs energies of transfer of these salts from water to water-dmf mixtures have been calculated from the solubilities of the salts in these mixtures. The transfer free energies of the salts were split into their ionic contributions by using the transfer-free energy of the silver ion in these mixtures obtained on the basis of negligible liquid junction potential (nLjp) method from independentemf measurements. The solvent transference number, Δ ofdmf, was determined byemf measurements using a suitable galvanic cell with transference. The results have been interpreted in terms of a heteroselective solvation of the salts with the silver ion selectively solvated bydmf and the anions by water.