Raman scattering has been used to study ionic interactions in trivalent M(CF3SO3)(3)-PEO complexes, M=Eu3+, Nd3+ and Ce3+. Both solvated ions and cation-anion pairs/multiplets were found, and, in the case of Nd3+ and Ce3+ complexes, the spectra suggest more complicated configurations of combined cation-anion-polyether coordinations. The findings are discussed in terms of the cationic charge density. Intense luminescence was observed in the Eu3+ complexes which converted blue laser light into red radiation. The well defined luminescence spectra support the concept of several cationic sites in these complexes.