Dividing-wall columns are a promising separation device in terms of energy efficiency because they are suitable for the complete separation of ternary mixtures. The increased application of this progressive technology is based on reduced capital and operating costs. Although several articles have already been published in the field of dividing-wall columns, reliable knowledge is still missing concerning the dynamics of this separation process. To bridge this gap, experimental data on the process dynamics of dividing-wall columns around a steady-state operating point are presented herein, together with extensive model validation of the transient behavior of dividing-wall columns. Furthermore, the process model was successfully compared with experimental data from a production-scale dividing-wall column, which emphasizes the validity of the model. Thus, the validated process model serves as a virtual plant and can be used to develop and test future process control structures. Moreover, the knowledge gained from this study will help to increase the acceptance of dividing-wall columns in industry.