The vapor pressures of methylcarbamate (MC) and methyl n-phenyl carbamate (MPC), at different temperatures ranging from (341.45 to 418.45) K, have been measured using the quasi-static ebulliometric method. The experimental data were fitted to the Antoine equation with the overall average absolute deviation of pressure of 0.06 kPa. Isobaric vapor liquid equilibrium (VLE) data were also determined for the MC and MPC system at (1.00, 2.00, 4.00, 6.00, and 8.00) kPa by the same method and were correlated with nonrandom two-liquid (NRTL) and Wilson models. The both model parameters were obtained with the overall average absolute deviation of temperature 0.82 K and 0.81 K. The relative volatility of the binary system was calculated and was more than 1 by far, indicating that high-purity MPC can be obtained from the binary mixture by distillation technology.