In this study, the quasi-static ebulliometric method was used to measure both of the vapor pressures of methyl N-phenyl carbamate (MPC), and the isobaric vapor-liquid equilibrium (VLE) data of the aniline and MPC binary system. The measured vapor pressure data of MPC, at different temperature ranging from 369.60 to 389.54 K, fitted well with the Antoine equation. The VLE data for the aniline and MPC system at (2.00, 4.00, 6.00, 7.00 and 8.00) kPa were correlated by both of nonrandom two-liquid (NRTL) and Wilson models. The parameters of the two models were obtained by regressing the experimental data, with the absolute temperature deviations of 0.54 K and 0.53 K, respectively. The relative volatility of the binary system calculated was all far more than 1, which gives the conclusion that the high purity MPC can be separated from aniline and MPC binary system by rectification or distillation technology. (C) 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.