We present a detailed study of the dynamic processes present in the lithium ionic conductor lithium trifluoromethane sulfonate, LiCF3SO3. Using Li-7-, O-17- and F-19 solid state NMR line shape analysis and T-1-NMR, the anionic (CF3- and SO3-reorientation) and cationic dynamics (Li motion) could be studied separately. Whereas the CF3- and SO3 reorientations are active at ambient temperatures and not correlated to the cation motion, the NMR data indicate a strong correlation between the Li motion and the reorientation of the complete triflate anion. (c) 2005 Elsevier B.V. All rights reserved.