The solid-state structure of the TMEDA complex offluorenyllithium is investigated by the6Li−13C REDORNMR experiment. The REDOR experiment was performed on6Li-enriched samples with detection of thenaturalabundance 13C-signal. This simplifies theinterpretation of the data and also the sample preparation. Thedipole−dipole couplings between the 6Li cation and the13C nuclei, determined with the REDOR sequence, yieldsdirectstructural information. The distance information is also helpfulwhen assigning the solid-state 13C NMRspectrum.The position of the Li cation is determined to within ±0.2 Å(with respect to the fluorenyl framework).