Multi-input multi-output (MIMO) dynamic matrix control (DMC) technique is applied to control steam temperatures in a large-scale ultrasupercritical once-through boiler-turbine system. Specifically, four output variables (i.e., outlet temperatures of platen superheater, finish superheater, primary reheater, and finish reheater) are controlled using four input variables (i.e., two spray valves, bypass valve, and damper). The step-response matrix for the MIMO DMC is constructed using the four input and the four output variables. Online optimization is performed for the MIMO DMC using the model predictive control technique. The MIMO DMC controller is implemented in a full-scope power plant simulator with satisfactory performance.