The anoxic–oxic (A/O) municipal wastewater treatment plant (WWTP) of Manresa (Catalonia, Spain) was studied for a possible conversion to an anaerobic/anoxic/oxic (A2/O) configuration to promote enhanced biological phosphorus removal. The control structure had to be redesigned to satisfy the new necessity to control phosphorus concentration, besides ammonium and nitrate concentrations (main pollutant concentrations). Thereby, decentralized control structures with proportional-integral-derivative (PID) controllers and centralized control structures with model-predictive controllers (MPC) were designed and tested. All the designed control structures had their performance systematically tested regarding effluent quality and operating costs. The centralized control structure, A2/O-3-MPC, achieved the lowest operating costs with the best effluent quality using the A2/O plant configuration for the Manresa WWTP. The controlled variables used in this control structure were ammonium in the effluent, nitrate at the end of the anoxic zone and phosphate at the end of the anaerobic zone, while the manipulated variables were the internal and external recycle flow rates and the dissolved oxygen setpoint in the aerobic reactors.