The proton and natural abundance carbon-13 NMR spectra of (+/-)-3-butyn-2-ol enriched in the S enantiomer (ee = 72%) and oriented in the chiral nematic liquid crystalline phase of [poly(gamma-benzyl-L-glutamate)/deuterochloroform] have been obtained and analyzed. The residual H-1-H-1 and H-1-C-13 dipolar couplings were corrected for the effects of molecular harmonic vibrational motions and used to determine the r(alpha) structure and the five independent order parameters, S-alpha beta, for each enantiomer. It is shown that the data is consistent with the two enantiomers having an identical r(alpha) structure, but the order matrices differ in both the magnitudes of their elements and the orientation of their principal axes.