The orientational ordering of three 4′-cyanophenyl-4-alkylbenzoates (with number of carbons in the alkyl chain,n= 6,7 and 8; hereafter abbreviated asn-CPBs) has been investigated by13C NMR. The order parameters of different molecular segments in the nematic phase of then-CPBs were determined by the two-dimensional technique of separated local field (SLF) spectroscopy combined with off-magic-axis, variable-angle spinning (VAS) of the sample. The carbon-13 chemical shifts for each carbon nucleus in these compounds were determined by slowly spinning the sample parallel to the applied magnetic field. The order parameters obtained from SLF/VAS studies are linearly related to the corresponding anisotropic carbon-13 chemical shifts. These results provide a convenient way to obtain the order parameters for other homologous members of this liquid crystal series by direct measurement of only their carbon-13 chemical shifts in conjunction with the observed linear relationship between order parameters and chemical shifts.