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The addition of plasticizer to the polyethylene oxide (PEO)–ammonium fluoride (NH₄F) polymer electrolytes has been found to result in an increase in conductivity value and the magnitude of increase has been found to depend upon the dielectric constant of the plasticizer used. The addition of dimethylacetamide as a plasticizer with dielectric constant (ϵ=37.8) higher than that of PEO (ϵ∼5) results in an increase of conductivity by more than three orders of magnitude whereas the addition of diethylcarbonate as a plasticizer with dielectric constant (ϵ=2.82) lower than that of PEO does not enhance the conductivity of PEO–NH₄F polymer electrolytes. The increase in conductivity has further been found to depend upon the concentration of plasticizer, the concentration of salt in the polymer electrolyte as well as on the dielectric constant value of the plasticizer used. The conductivity modification with the addition of …