Polymer electrolytes have received much attention since the concept of all solid-state batteries had been introduced. Electrolyte structure depends on the nature of the salt and its concentration, which both have considerable impact on the state of the electrolyte, Their effects on properties like conductivity, glass transition temperature (TO, provide useful information on diffusive phenomena in such materials. Up to now, the strategy has been oriented to reach the maximum amorphicity of the polymer and the lowest T, In contrast, we report here studies of salt-polymer complexes in which the solute is designed to induce some local order in the electrolytes (alignment, point or mirror symmetry). The influence of solute concentration and of the counter-cation is reported, Physico-chemical characterisation has been obtained by using conductivity, differential scanning calorimetry, and optical activity.