The orientational ordering of a series of 4-alkenyl-substituted bicyclohexyl liquid crystals was studied by natural abundance13C NMR spectroscopy. A combination of the methods of variable angle spinning (VAS) and separated local field spectroscopy (SLF) was used. Rapid sample spinning about an axis forming an angle of about 65° with respect to the magnetic field forces the nematic director to align parallel to the spinnin axis, leading to narrow peaks in the13C NMR spectrum. The two-dimensional NMR spectroscopic method SLF allows the observation of decoupled13C signals in the ω2dimension and first-order C-H splitting patterns in the ω1dimension, from which the C-H dipolar coupling constants for individual pairs of nuclei can be obtained. Then, the order parameters for different molecular segments can be calculated. The method was applied to five different 4-alkenyl-substituted cyanobicyclohexanes. For the compounds studied, the dependence of the ring order parameters on the alkenyl chains shows the same trend as the melting and clearing temperatures and the elastic constants.