2H NMR measurements of deuterated solute molecules in a poly(γ-benzyl-L-glutamate) (PBLG)/dichloromethane or chloroform liquid-crystalline solvent are presented. The quadrupolar splittings of solutes were determined in order to make good use of them in stereochemical and conformational analyses. The results obtained for achiral model compounds of different size, symmetry, shape, and flexibility are interpreted qualitatively. Emphasis is put on the routine application of this technique. Advantages of working in such lyotropic liquid-crystalline solvents, namely the enhanced signal dispersion or the rich information content of the 2H spectra compared with those recorded in isotropic media, are emphasised.