Recent applications of solid-state NMR to the characterisation of nucleic acid systems are reviewed. Developments in NMR methodology and DFT-based first-principles calculations have led to the emergence of “NMR crystallography”, where solid-state NMR provides information on local structure and dynamics that complements information on periodic ordering and overall structure provided by traditional diffraction crystallography. The solid-state NMR is shown to provide direct information on hydrogen-bonding arrangements, metal ion interactions and local molecular dynamics that is difficult to obtain by other techniques, including solution-state NMR.