In this contribution we present studies on the mechanism of ion transport in crystalline solid electrolytes employing a range of different solid state nuclear magnetic resonance (NMR) experiments. The first part is devoted to the elucidation of a possible correlation of cation transport and anion reorientation in the dynamically disordered rotor phases of alkali trifluoromethane sulfonates MCF3SO3 (M = Li, Na) employing Li-7, C-13, O-17 and Na-23 NMR line shape analysis, whereas the second part focuses on the tracking of cation diffusion pathways in the hexaoxometalate Li7TaO6 utilizing Li-6 1D and 2D exchange MAS NMR approaches. (c) 2006 Elsevier B.V All rights reserved.