In this work, isobaric vapor–liquid equilibrium (VLE) measurements were conducted for the binary systems of prop-2-en-1-ol (1)–hexan-2-ol (2), prop-2-en-1-ol (1)–hexan-2-one (2), hexan-2-one (1)–hexan-2-ol (2), prop-2-en-1-ol (1)–4-methyl-pentan-2-ol (2), prop-2-en-1-ol (1)–4-methyl-pentan-2-one (2), and 4-methyl-pentan-2-one (1)–4-methyl-pentan-2-ol (2) to assist with the design of the separation process by distillation. Measurements were determined using Fischer VLE 602 equipment at 101.32 kPa. The thermodynamic consistency of the measured VLE data was validated by modified Herington, Van Ness, pure component consistency, and Redlich–Kister total area tests. Moreover, data sets were correlated using the nonrandom two-liquid (NRTL), universal quasichemical (UNIQUAC), and Wilson thermodynamic models to obtain the binary interaction parameters using the Aspen Plus V11 commercial software. The root-mean-square deviations (RMSDs) of the equilibrium temperature (T) and the vapor mole fraction (yi) were less than 0.24 and 0.0089, respectively, which indicate that these three thermodynamic models can be used to correlate the six binary systems and therefore they can be employed for the development and optimization of the separation process.