Many by-products are generated in the process of oxidizing cyclohexene to produce 1,2-epoxycyclohexane by hydrogen peroxide, including cyclohexanol, cyclohexanone, etc. To obtain high-purity 1,2-epoxycyclohexane, the by-products and unreacted cyclohexene must be removed through rectification, in which the vapor-liquid equilibrium (VLE) data of the system are needed. In this study, the VLE data of cyclohexene-cyclohexanol system were studied at 101.3 kPa using an improved EC-2 VLE still. The thermodynamic consistency of the data was examined by Herington's method. The results obtained were exemplary. The VLE data were correlated by the Wilson equation. The difference between the calculated values and the experimental data is minor, indicating that the VLE data are suitable for engineering design.