Bekiaris et al. (Ind. Eng. Chem. Res. 1993, 32 (9), 2023) explained the existence of multiple steady states in homogeneous azeotropic distillation on the basis of the analysis of columns with infinite reflux and infinite length (infinite number of trays). They showed that the predictions of multiple steady states for such infinite columns have relevant implications for columns of finite length operated at finite reflux. The first experimental verification of the existence of such multiple steady states was published by Guttinger et al. (Ind. Eng. Chem. Res. 1997, 36 (3), 794). Using an industrial pilot column without an automatic control system, they confirmed the existence of two stable steady states for the ternary homogeneous system methanol-methyl butyrate-toluene. That is, two different column profiles occurred for the same operating parameters, feed flow rate, and feed composition. In this paper, experiments for the same ternary system are described which show the existence of a third unstable steady state. The unstable steady state is stabilized with PI control. Furthermore, the transition from an unstable to a stable operating point is demonstrated when the control action is removed.