Standard transfer free energies of sodium and cupric perchlorates in water-acetylacetone solvent system have been determined by electromotive force measurements of galvanic cell and these energies of sodium and cupric ions in this solvent system have been evaluated by the tetrabutylammonium tetraphenylborate assumption as the extrathermodynamic procedure. Standard transfer free energy values of sodium and cupric ions from water to acetylacetone solvent were 5.09 and 4.16 kcal/mol at 25${circ}C$, respectively. These values mean that acetylacetone is much weaker donor solvent to sodium and cupric ions than water. The standard transfer free energy value of cupric ion from water to mixture solvents which contain small amount of acetylacetone is changed by an unusual form. This is because of the chelate formation effect of acetylacetone to cupric ion.