The 27Al NMR spectra of calcium tungstate aluminate sodalite (CAW), Ca 8[Al 12O 24](WO 4) 2, and the 23Na NMR spectra of sodium aluminosilicate sodalites of general composition Na 8[Si 6Al 6O 24]A 2 with A = B(OH) 4 − (SBS), SCN − (SRS) and A 2 = SO 4 2− (SSS), MoO 4 2− (SMS) have been measured using magic-angle spinning (MAS) and double-rotation (DOR) techniques. Rotor synchronized pulse excitation is applied in the DOR experiments. Dramatic line narrowing is observed in the DOR spectra of all samples. The 27Al DOR NMR spectra of CAW measured at 9.4 and 11.7 T and spinning rates of 800–1150 Hz of the outer and 5 kHz of the inner rotor show seven sharp central lines accompanied by a manifold of spinning sidebands. These lines correspond to the seven crystallographically inequivalent Al sites of the CAW framework derived from X-ray structure analysis. From the difference of the line positions in the 9.4 and 11.7 T spectra the quadrupole coupling constant, QCC, quadrupole induced shift, σ qs, and isotropic chemical shift, σ cs, of each Al site have been calculated. QCC values in the range of 5 to 9 MHz are obtained which reflect the strong tetragonal distortion of the AlO 4 tetrahedra in CAW. δ cs shows only small changes in the range between 74.4 and 77.2 ppm. A tentative assignment of all lines to the distinct Al sites is derived from the correlation between QCC and a “shear strain parameter” describing quantitatively the distortion of the AlO 4 tetrahedra. The 23Na DOR NMR spectrum of the low-temperature form of SBS reveals the presence of four inequivalent sodium sites which confirms the tetragonal space group P42 1c proposed for this structure. The 23Na DOR NMR spectra of the sodium aluminosilicate sodalites SSS, SMS and SRS confirm the assumptions made in the computer simulations of the corresponding 23Na MAS NMR spectra.