Abstract Isobaric (vapour+liquid) equilibria were determined at p =101.3 kPa for (methanol+butyl acetate), (methanol+isobutyl acetate), (vinyl acetate+butyl acetate), and (vinyl acetate+isobutyl acetate). The thermodynamic consistency of the experimental data was checked by using a modified Dechema test. The activity coefficients were correlated with Margules, van Laar, Wilson, NRTL, and Wilson equations. Among the solvents chosen as potential extractive distillation entrainers, none shows azeotropy. It was found more appropriate to use butyl acetate as solvent for the extractive distillation from an economical perspective.