Successful tools for the study of structural and dynamic problems in solid state ionic materials are electric and magnetic resonance and relaxation as well as the ITC (TSD) technique. Some applications of these structure-sensitive methods on fluoro-conducting systems in a wide range of temperature are demonstrated. The advantages, especially of the PMFG-NMR techniques, for a direct study of diffusion coefficients in these substances are shown. Correlations between local structures and ion conductivities are established.