The measurement of diffusion parameters like activation energies and translational jump rates of small cations plays a key role in materials science. Especially the in-depth investigation of Li diffusion in ionic conductors is of great interest, because suitable ionic conductors are needed for, e.g., the development of new secondary ion battery systems. As the standard tracer method is not applicable to study Li diffusion due to the lack of a suitable radioactive isotope, Li diffusion is alternatively probed by solid state NMR techniques. With the different NMR methods being available, diffusion processes can be studied on different length- and timescales. In the present paper we use two-time spin-alignment echo (SAE) NMR for the direct, i.e., model independent, measurement of extremely small translational Li jump rates. To this end, different crystalline and glassy ion conductors like LixTiS2, Li4SiO4 as well as LiNbO3 served as model substances to reveal the special features of this technique. SAE-NMR, which was originally developed for deuterons, has also been applied in a few cases to spin-3/2 nuclei, like Li-7, before. The corresponding correlation functions yield not only information about diffusion parameters but also about geometric properties of the diffusion pathways, making SAE-NMR a powerful method which complements well-established NMR techniques. (c) 2006 Elsevier B.V. All rights reserved.