Synthetic lepidolites and Li-muscovites have been investigated using two-dimensional cross-polarisation heteronuclear correlation magic-angle-spinning solid-state nuclear magnetic resonance spectroscopic experiments. All results show a related ordering of the tetrahedral and octahedral sheets, with more tetrahedral Al sites close to Al-rich octahedral sites preferably coordinated by OH^- anions and Si-rich tetrahedral regions close to Li-rich octahedral sites preferably coordinated by F^- anions.