Dividing wall columns (DWCs) are practical, effective, and promising among distillation process intensification technologies. Nonlinear model predictive control (NMPC) schemes are developed in this study to control the three-product DWCs. As these systems are intensely interactive and highly nonlinear, NMPC may be more suitable than the traditional PI control. The model is established based on Python and Pyomo platforms. As the original mathematical model of the column section is ill-posed, index reduction is used to avoid a high-index differential-algebraic equation (DAE) system. The well-posed index-1 system after index reduction is employed for the steady-state simulation and dynamic control in this study. Case studies with three DWC configurations to separate the mixture of ethanol (A), n-propanol (B), and nbutanol (C) show that the NMPC performs very well with small maximum deviations and short settling times. This demonstrates that the NMPC is a feasible and very effective scheme to control three-product DWCs.