From variable temperature NMR studies of trans1and cis24-cyanocyclohexanols d4−2, 2, 6, 6, the conformational enthalpy values for CN (-0.84 kJ mol−1) and OH (-3.03 kJ mol−1) substituents are obtained together with the activation free enthalpy differences at the coalescence temperatures (ΔG≠1= 47.74 and ΔG≠2= 47.65 kJ mol−1). The structures obtained by the studies of 1r, 3c, 4t3and 1r, 3c, 4c43-tert-butyl 4-cyanocyclohexanols d4−2, 2, 6, 6 agrees with a distorted chair conformation due to the tert-butyl cyano gauche interaction.