A study of the thermal and mechanical characteristics of polyethylene oxide-Fe(SCN)3 complexes shows the existence of structures which can be described by considering a crystalline phase of pure polyethylene oxide (PEO) and an amorphous phase of PEO with dissolved salt. Increasing salt contents decrease the content of crystals, favoring the formation of complexes with a high degree of noncrystallinity as a result of strong polymer-salt interactions which tend to enhance the distortion degree of the polymeric skeleton. The microscopic homogeneity of the complexes is also confirmed by the presence in the thermal and mechanical spectra of single glass transitions, which shift to higher temperatures with increasing salt content. Two molecular relaxations are present in the mechanical behavior of these systems, the gamma- and the alpha(a)-processes at low and high temperatures, respectively, and show a relaxation strength which increases with decreasing degree of crystallinity of the polymer up to a X approximately 0.10 molar fraction. Both relaxations exhibit a marked nonexponentiality which has been well accounted for in terms of a gaussian distribution of relaxation times for the gamma-process and of the Kolrausch-Williams-Watt exponential function for the alpha(a)-process. In the glassy region, the elastic modulus E’ reveals a linear temperature dependence which has been interpreted as arising from the anharmonicity of the anharmonicity parameter, which has been ascribed to the influence of the "free volume" in determining the thermal expansivity