Pervaporation-fractional condensation (PVFC) is a new type of coupling process developed for high purity recovery of high boiling organic compounds in low concentration aqueous solutions.On the basis of experimental data, the thermodynamic processes of PVFC and traditional extractive distillation were analyzed by the model of non-random two liquid (NRTL) within the Aspen Plus software, with the emphasis on the influence of operating temperature on the product quality and yield, as well as the energy consumed by the two kinds of processes.The mechanism of obtaining high purity furfural by the PVFC process was also revealed.The results show that the energy consumption by the PVFC process was only 50% of that by the extractive distillation process.However, the purity of the product by the PVFC process, 99.9% (experimental value) , was higher than that by the extractive distillation process, 97%.Compared with the traditional process, the PVFC coupling process needs less unit equipments, not only saving energy consumption but avoiding the use of extracting agent also.Therefore, it is a good application for high purity recovery of high boiling point organic compounds which are easy to form azeotropic system.