Picturing the ion-chain local configuration of polyether-salt materials as forming oxygen-lined helical turns, with the cation located within the polymer cavity, the local environment of each cation is described in terms of a first coordination shell, characterized by the cation and by its nearest oxygen ligands. The interaction energy between nearest shells, epsilon, for the eutectic concentration of europium-based poly(ethylene oxide), PEG, electrolytes, is calculated by two separate processes : One relating the empirical value of the nearest-ligands local-field energy with the variation of Eu3+ concentration, n, and the other involving a two-electron polarization potential. This last procedure, besides determining the minimum iutershells distance for the eutectic phase, permits the number of Eu3+-nearest oxygens to be fixed. The Value obtained by the first procedure was epsilon = 554.2 cm(-1). while by the second, were epsilon = 520.3 cm(-1); for 10 nearest oxygens, and epsilon = 572.4 cm(-1); for 11 oxygens, for a mean radius of the first coordination shell (R) over bar = 2.4 Angstrom and a minimum distance between nearest shells R(0) = 5.3 Angstrom. This model of chains of interacting coordination shells is extended to other polyether-salt complexes modified by mono and divalent cations. The corresponding two-electron interaction potential is calculated for a few monovalent-based crystalline PEG, complexes, while for noncrystalline divalent electrolytes only an upper limit is estimated.