Isobaric vapor-liquid equilibria were determined at 101.3 kPa for methanol + pentyl acetate, methanol + isopentyl acetate, and vinyl acetate + pentyl 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. None of the systems shows azeotropy. Pentyl acetate is a potential extractive distillation entrainer of the azeotropic mixture methanol + vinyl acetate.