Vapor-liquid equilibrium (VLE) data for methanol + methyl acetate + 1-octyl-3-methylimidazolium hexafluorphosphate ([OMIM][PF(6)]) at 101.3 kPa were measured. The experimental VLE data were correlated by the nonrandom two-liquid (NRTL) activity coefficient model, and the binary parameters were obtained. The results show that the ionic liquid [OMIM][PF(6)] produces a notable salting-out effect, which enhances the relative volatility of methanol to methyl acetate. The effect of [OMIM][PF(6)] on methanol + methyl acetate system was compared with that of o-xylene.