For separation of the azeotropic mixture of isopropyl alcohol and methyl ethyl ketone by extractive distillation with dimethyl sulfoxide as an extractant, the isobaric vapor−liquid phase equilibrium (VLE) data for the binary mixtures (isopropyl alcohol + dimethyl sulfoxide) and (methyl ethyl ketone + dimethyl sulfoxide) and the ternary mixture (isopropyl alcohol + methyl ethyl ketone + dimethyl sulfoxide) were ascertained at a temperature range from 352.75 to 463.79 K and 101.3 kPa. The coherence of the measured VLE data was checked using the van Ness method and Wisniak's L− W method. The determined VLE data for the mixtures was correlated by the Wilson, UNIQUAC, and NRTL equations. The parameters pertaining to the models were regressed for the binary systems. The findings demonstrated that the three equations were capable of fitting the ascertained VLE data. The VLE data of the ternary mixture comprising isopropyl alcohol, methyl ethyl ketone, and dimethyl sulfoxide were forecasted utilizing the NRTL, UNIQUAC, and Wilson equations, employing the fitted model parameters. The results displayed an agreement between the collected data and the computed values.