This work investigated the full design, startup, operation, and control of a Kaibel divided-wall column (KDWC) for a laboratoryscale KDWC. The KDWC is designed to separate mixtures of methanol, ethanol, n-propanol, and n-butanol on the basis of a rigorous model. Effective steady-state and dynamic operation strategies are then proposed to control the practical operation of the KDWC. The proposed startup operation strategy, including total reflux, batch rectification, and continuous rectification procedures, leads to a steady state, and the steady-state design method is verified through steady-state experiments. The dynamic control strategy including a four-temperature control loop is further proposed and shows effective and precise dynamic control performance, recovering the four products to the specified values in the presence of ±20% feed disturbances. This work provides deep insight into the realization and control of a practical KDWC and will increase the possibility of industrial achievement and optimal operation of the KDWC.