This work explores the dynamic and control behavior of dividing wall distillation columns from two different steady‐state design approaches (molecular tracking and optimization method) for three different mixtures. The controllability of the six design cases was evaluated using singular value decomposition and the closed‐loop performance was evaluated using integral absolute error in Aspen Dynamics. The results demonstrate that the side‐draw location obtained by molecular tracking (MT) provides optimal controllability. As a result, there is a slight advantage in control properties while obtaining designs by reducing the time to find the optimal solution through the MT method.