The isobaric vapor−liquid equilibrium (VLE) data of the binary system N,N-dimethylaniline + 2-amino-3-methylpyridine were collected at (5.158 and 8.041) kPa. The activity coefficients of the system were correlated with the Van Laar and UNIQUAC models. The results showed that the calculated values of the vapor phase mole fraction and boiling temperature by the two models agreed well with the experimental data. Furthermore, the activity coefficients at infinite dilution were also presented. The VLE data were shown to be thermodynamically consistent by both the Herington consistency and point consistency tests.