Isobaric vapor-liquid equilibrium (VLE) data for the ethyl acetate + methanol +1-ethyl-3-methylimidazolium diethylphosphate ([EMIM][DEPD and ethyl acetate + methanol +1-butyl-3-methylimidazolium dibutylphosphate ([BMIM][DBPD ternary systems were measured at 101.3 kPa with an improved all-glass single-cycle still. They were correlated with the nonrandom two-liquid (NRTL) model and were in good agreement with the correlated data. The results showed that the two ionic liquids (ILs) produced an obvious effect on the VLE behavior. With the addition of them into the azeotropic system, the relative volatility of ethyl acetate to methanol was enhanced. Moreover, the azeotropic point was eliminated as the mole fractions of [EMIM][DEP] and [BMIM][DBP] in the liquid phase were equal to 0.05 and 0.1, respectively. As for salting-out effect on ethyl acetate, [EMIM][DEP] outperforms [BMIM][DBP].