2H chemical shift anisotropies (CSAs) have been determined for the first time for polycrystalline samples employing 2H MAS NMR spectroscopy at high magnetic field strength (14.1 T). The 2H CSA is reflected as distinct asymmetries in the manifold of spinning sidebands (ssbs) observed for the two overlapping single-quantum transitions. Least-squares fitting to the manifold of ssbs allows determination of the 2H CSA parameters along with the quadrupole coupling parameters. This is demonstrated for KD2PO4, ND4D2PO4, KDSO4, KDCO3, α-(COOD)2, α-(COOD)2 · 2D2O, and boehmite (AlOOD) which exhibit 2H shift anisotropies in the range 13 ≤ δσ ≤ 27 ppm. For fixed values of the shift anisotropy and the 2H quadrupole coupling it is shown that the precision of the CSA parameters depends strongly on the asymmetry parameter (ηQ) for the quadrupole coupling tensor, giving the highest precision for ηQ ≈ 0. The 2H CSA parameters (δσ and ησ) are in good agreement with 1H CSA data reported in the literature for the corresponding protonated samples from 1H NMR spectra employing various homonuclear decoupling techniques. The determination of 2H quadrupole coupling parameters and 2H (1H) CSAs from the same 2H MAS NMR experiment may be particularly useful in studies of hydrogen bonding since the 2H quadrupole coupling constant and the CSA appear to characterize bond lengths in a hydrogen bond in a different manner. © 2003 Elsevier Inc. All rights reserved.