Data of vapor-liquid equilibria are essential in the design of a separation unit in the technology of cyclic alkene indirect hydration in the presence of formic acid. This work aims at measuring the vapor-liquid equilibria (VLE) data of the binary systems cyclohexanol + cyclohexyl formate and cyclopentanol + cyclopentyl formate under various pressures and to correlate these data by nonrandom-two liquid and universal quasichemical models to obtain binary interaction parameters that will be used for the design of a distillation unit. According to the best of our knowledge, the VLE of cyclopentanol + cyclopentyl formate binary system has not been published in the literature. Furthermore, the accuracy of the experimental data fitting for the system of cyclohexanol + cyclohexyl formate was compared to a previously published model. Moreover, the model obtained in this work was tested for data prediction under higher pressures, and good accuracy was achieved. Also, the thermodynamic consistency of the experimental data was evaluated by Fredenslund test, and the data fitting accuracy was calculated based on average absolute deviation and root-mean-square-error values.