The ion association behaviour observed in our earlier studies of a polyether electrolyte system at elevated temperatures, was reminiscent of the molar conductivity behaviour typical of low dielectric constant systems. Further investigation of this relationship has led to some suggestions about the types df ionic species present in the polymer electrolyte systems. FT-IR spectroscopy has been used in this work to contrast ion association in an amorphous polyether electrolyte with two liquid electrolytes, N,N-dimethylformamide and tetraethylenegylcol dimethylether, containing lithium trifluoromethan sulfonate.