Vapor-liquid equilibrium data of chloroform-N,N-dimethylformamide (DMF) system are first determined at 101.3 kPa by using the equilibrium distiller. The binary VLE data are correlated by NRTL, UNIQUAC and Wilson models respectively. The activity coefficients are obtained by the simplex method. Average relative deviations between the calculated values with the three models and the experimental data of gas phase mole fraction are all less than 2.24%, and average relative deviations between calculated values and the experimental data of temperature are all less than 0.62%. The root mean square deviations (RMSD) of compositions and temperature are less than 0.005 and 0.7 K, respectively. Thermodynamic consistency of the experimental data is tested according to Herington method. It is demonstrated that calculated results of NRTL, UNIQUAC and Wilson equations are all in good agreement with the experimental data, and that azeotrope behavior is not found for the binary system of chloroform + DMF The results not only provide the basis for analysis and design of distillation process, but also promote the development of new technology to recover DMF from wastewater. (C) 2009 Elsevier B.V. All rights reserved.