We report tetrahydroborate aluminosilicate, gallosilicate and aluminogermanate sodalites studied by B-11, H-1 and Na-23 MAS NMR spectroscopy. The spectral parameters are consistent with the local environments of each investigated nucleus obtained from the crystal structures. The B-11 MAS NMR spectra exhibit a sharp narrow line at about -49.0 ppm, which is assigned to BH4- enclathrated into the sodalite framework matrix. The lineshape of the signal shows no quadrupolar interactions due to discreteness and high symmetry of the BH4- unit as well as possible fast dynamic site exchange of hydrogen atoms. The Na-23 MAS NMR signals also show a narrow Gaussian lineshape, which clearly indicates a single type of sodium coordination, and a centrosymmetrical charge distribution around the sodium atom. The 1H MAS NMR spectra can clearly distinguish between hydrogen in BH4- anions (-0.6 ppm), H3O2- anions (1.2 ppm) and H2O molecules (5.0 ppm). The structural properties of BH4- intercalation into socialite framework matrix help connect the microporous materials to hydride-containing A, X and Y type zeolites. (c) 2009 Elsevier Ltd. All rights reserved.