The orientational order of two liquid crystals , namely, 6 [4 (4 nitrophenylazo)phenyloxy] hexyl diethanolamines(C6) and 10 1 bromo[4 (nitrophenylazo)phenyloxy] alkane(B10) was studied by means of 2H NMR spectroscopy with hexamethylbenzene d 18 as the probe molecule. The results show that the directors in the smectic A phase of C6 and the nematic phase of B10 could be aligned, which was parallel to the magnetic field. The orientational order parameter of the solute molecules in C6 was about 0.2, while it is only 0.1 in B10, which is expected because the more ordered smectic phase tends to align solute molecules to a high level. Compared to the orientational order parameter of the solute in the SmC phase of 4[3,4,5 tris(4 dodecyloxybenzyloxy) benzoyloxy] 4 (4′ dodecyloxybenzoyloxy)biphenyl (Ⅰ) ( P 2=0.14 ), it is larger in SmA phase of C6. The relatively higher orientational order parameter of the solute in C6 is attributed to the formation of intermolecular H bonds in the SmA phase of C6. The orientational order of two liquid crystals, namely, 6 [4 (4 nitrophenylazo) phenyloxy] hexyl diethanolamines (C6) and 10 1 bromo [4 (nitrophenylazo) phenyloxy] alkanes (B10) was studied by means of 2H NMR spectroscopy with hexamethylbenzene d The results show that the directors in the smectic A phase of C6 and the nematic phase of B10 could be aligned, which was parallel to the magnetic field. The orientational order parameter of the solute molecules in C6 was about 0.2 , while it is only 0.1 in B10, which is expected because the more ordered smectic phase tends to align solute molecules to a high level. Compared to the orientational order parameter of the solute in the SmC phase of 4 [3,4,5 tris (4) dodecyloxybenzoyloxy) biphenyl (I) (P 2 = 0.14), it is larger in SmA phase of C 6. The more higher orientational order parameter of the solute in C6 is attributed to the fo rmation of intermolecular H bonds in the SmA phase of C6.