In the present paper, an intensive analysis of simulation of conventional distillation and extractive distillation to separate a mixture of toluene and heptane (toluene-heptane azeotrope) has been performed. A literature review has been performed for both conventional and extractive distillation and also the advancements and new techniques developed to increase the efficiency of both processes. Aspen Hysys was used as the simulator of choice for simulating both conventional distillation and extractive distillation, whereas Aspen Plus was used to compute the VLE data for interaction of the three compounds with each other. Comparison of the energy consumed by both the processes to achieve the same separation efficiency was done. Cost analysis was performed by using aspen cost analyzer. Cost efficiency was used as the criteria to determine the best process. Extractive distillation was determined to be costing less than13⁄ times the price of conventional distillation process. Hence extractive distillation is clearly the more economical process.