The distillation based separation can be extremely complex if highly non-ideal mixtures are to be separated. In spite of different successfully applied unit operations there is still possibility to improve distillation technique and widen its toolbar. A new improvement in this area is the introduction of the extractive heterogeneous-azeotropic distillation (EHAD). This unit operation includes the merits of the extractive and heterogeneous-azeotropic distillations in one unit without an extra material addition. In spite of the complexity of this unit operation it can be efficiently applied and complex separation technologies can be simplified with its application. The separations of ternary and quaternary mixtures from the fine chemical industry show both in the modelled and the experimental results that the extractive heterogeneous-azeotropic distillation is an efficient tool of this area. Demonstrating the accuracy of EHAD, the separation of methanol–ethyl-acetate–water and ethanol–ethyl-acetate–water mixtures are examined and the EHAD is compared with conventional distillation techniques. These separation processes are rigorously modelled and optimized with dynamic optimization method in professional flowsheeting environment. The objective function is the total annual cost but the energy consumption is also investigated. The modelling results are verified with laboratory experiments, too. It can be concluded that the extractive heterogeneous-distillation is a capable method for the separation of these highly non-ideal mixtures.