Five sets of cis- and trans-substituted cyclohexanols were used for reaction with thianthrene cation radical perchlorate, namely, cis- and trans-cyclohexane-1,2-diol, cis- and trans-2-methyl-, 3-methyl-, and 4-methylcyclohexanol, and cis,cis- and trans,trans-3,5-dimethylcyclohexanol. Reaction in CH2-Cl2 solution and precipitation with ether gave the corresponding crystalline 5-(cyclohexyloxy)-thianthreniumyl perchlorate salts. The configuration of each salt in CDCl3 was shown by 1H and 13C NMR spectroscopy to correspond with the configuration of the cyclohexanol from which it was made. X-ray Ortep diagrams of four of the salts confirmed the structure deduced from NMR spectroscopy. In the NMR, inequivalence of the 1H and 13C signals from the thianthreniumyl 4-and 6-, 1- and 9-, 2- and 8-, and 3- and 7-positions was found when the 1′-position of the cyclohexyl ring was stereogenic. In the four Ortep diagrams, the orientation of the S-O bond was psuedoaxial. Thermal decomposition of the salts made from the monosubstituted cyclohexanols at 100°C in CH3CN solution gave products consistent with the assigned structures.