The vapor liquid equilibrium (VLE) data at the constant pressure of P = 1 bar were determined for binary mixtures consisting of cyclohexanone + 2-cyclohexen-1-one and cyclohexanol + 2-cyclohexen-1-one. The thermodynamic consistency of the VLE data was verified with the Wisniak's and area tests, with positive results. Experimental VLE data were fitted to the nonrandom two-liquid (NRTL) model to obtain the NRTL binary interaction parameters for the mentioned mixtures. A good fit between experimental and predicted data was found. Finally, the binary interaction parameters obtained were validated in a steady state operation, where a ternary mixture of cyclohexanone, cyclohexanol, and 2-cyclohexen-1-one was fed to a packed distillation tower. The experimental results were satisfactorily predicted and simulated by the RadFrac block included in Aspen Plus v8.4 software. Therefore, the binary interaction predicted can be used to model the behavior of the mixture under continuous operation conditions.