The steady-state multiplicity in azeotropic distillation processes has been theoretically predicted and verified experimentally for decades. However, it is a tough task to detect all the steady-state solutions. The purpose of this article is 2-fold: first, it provides a systematical study on the multiplicity in homogeneous azeotropic distillation with intermediate entrainer and a novel strategy is proposed to find all the steady-state solutions using "Design Specs/Vary" in Aspen Plus. Operating on the unstable steady-state branch benefits both energy saving and reducing capital investment with the product quality specified. Because of the great benefits that operating on the unstable steady-state branch offers, the second purpose is to present suitable control schemes to stabilize the operating point on the unstable steady-state branch to achieve robust control.