Azeotropic distillation has wide application in chemical process industry and petrochemistry for separation of components of mixtures with close boiling points or azeotropic systems. Because of all that, their design is complex and requires very good understandg the thermodynamic properties, vapor – liquid equilibrium (VLE), properties of mixtures and chemical properties of the components themselves. This paper shows the design of azeotropic distillation process with process synthesis framework i.e. three – step approach. This approach simplifies the design of any type of azeotropic distillation. Of course, nowadays it is quite easy to design the process with the help of computers.