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Viscosity and molar conductance of Bu4NBPh4, Bu4NClO4, [Cu(CH3CN)4]ClO4, NaClO4 and NaBPh4 have been measured in the concentration ranges 0.02 - 0.5 mol dm−3 and 0.0005 - 0.0065 mol dm−3 at 298.15 K in AN + DMF mixtures containing 0, 10, 20, 40, 60, 75, 80, 90, and 100 mol % DMF. The viscosity data have been analyzed by the extended form of the Jones-Dole equation in the form: (η/η0) = 1+AC1/2+BC+DC2 to evaluate B and D parameters and the conductance data by the Shedlovsky equation to evaluate Λo and KA values of the salts. Ionic viscosity B-coefficients (B±) and ionic molar conductances (λ◦ i) have been calculated by using Bu4NBPh4 as a reference electrolyte. Solvated radii (ri) for Na+, Cu+ and ClO4 − have been estimated by using Gill’s modification of Stokes’ law. The variation of B± and ri as a function of mol % DMF shows that both Na+ and Cu+ are highly solvated in AN + DMF mixtures over the entire composition region. The solvation passes through a maximum between 40 to 80 mol % DMF. Both Na+ and Cu+ are more strongly solvated between 40 to 80 mol % DMF. Cu+ is relatively more strongly solvated than Na+ in AN + DMF mixtures. ClO4 − shows poor solvation in AN + DMF mixtures.