Mass transfer operations are at the heart of every chemical engineering curriculum, as they are the basis of separation procedures extensively used in the chemical industry. Distillation, which involves mass transfer between vapor and liquid phases, is, by far, the most extended separation practice. However, the presence of azeotropes in most of the mixtures with industrial interest complicates the process analysis due to tedious and complex calculations, even in the simplest case of binary mixtures. Moreover, the need for recycle streams makes convergence and variables specification very difficult as compared with the separation of nonazeotropic mixtures. Initial training in process simulators results fundamentally in high‐quality chemical engineering teaching programs. It yields a better understanding of enhanced distillation and entails the use of professional tools highly demanded by employers. This paper reports how the use of the commercial simulator Aspen Plus can help students explore azeotropic distillation by their own, and thus enables looking into aspects which are beyond the scope of problems solved by hand.