The process for aromatics recovering with N-formylmorpholine (NFM) by extractive distillation has been widely applied in petrochemical and coal tar industries, and the research for vapor-liquid equilibrium (VLE) of NFM and toluene were very important in design and optimization of rectifying tower. The VLE data of above binary system was determined using an improved VLE equipment EC-2 under 101.33 kPa, which have pass the thermodynamic consistency test of Herington, and were correlated with the NRTL and UNIQUAC models, and corresponding binary interaction parameters for the two models were obtained. The VLE curves predicted by the above model parameters agree more well with the experimental data than that predicted by literature model gained from data under 60 ℃. The VLE data and model parameters obtained above are essential for the engineering design of N-formylmorpholine-aromatics distillation processes.