Standard Gibbs energies of transfer have been determined for copper(II) iodate, benzoate and formate at 30°C in methanol- dimethylformamide mixtures by solubility measurements. Single-ion transfer energies were obtained by using the negligible liquid junction potential assumption, along with relevant literature data, and are in excellent agreement with values estimated from the reference electrolyte ( tatb ) assumption. The results obtained indicate that all of these salts are heteroselectively solvated in these mixtures, with Cu2+ being preferentially solvated by dmf and the anions by MeOH. This model is consistent with calculations based on the quasi-lattice quasi-chemical theory of Marcus and with solvent transport numbers obtained from e.m.f . measurements.