Since the commercialization of rechargeable lithium-ion energy storage systems in the early 1990s, graphite intercalation compounds (GICs) have served as the number one negative electrode material in most of today's batteries. During charging the performance of a battery is closely tied with facile Li insertion into the graphite host structure. So far, only occasionally time-domain nuclear magnetic resonance (NMR) measurements have been reported to study Li self-diffusion parameters in GICs. Here, we used several NMR techniques to enlighten Li hopping motions from an atomic-scale point of view. Li self-diffusion in the stage-1 GIC LiC6 has been studied comparatively by temperature-variable spin-spin relaxation NMR as well as (rotating frame) spin-lattice relaxation NMR. The data collected yield information on both the relevant activation energies and jump rates, which can directly be transformed into Li self-diffusion coefficients. At room temperature the Li self-diffusion coefficient turns out to be 10−15m2s−1, thus, slightly lower than that for layer-structured cathode materials such as Lix≈0.7TiS2. © 2013 American Physical Society.