Vapor liquid equilibrium (VLE), liquid liquid equilibrium (LLE), and vapor liquid liquid equilibrium (VLLE) data were measured for the ternary mixture of 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIM] [PF6]), butan-1-ol, and butyl acetate. Results showed that the selectivity of butan-l-ol and butyl acetate can be enhanced by ionic liquid [OMIM] [PF6]. The experimental VLE and LLE data were correlated using NRTL model, and the calculated values agreed well with the experimental values.