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This paper presents a hierarchical intelligent decoupling control method for the gas collection process of three asymmetric coke ovens of an iron and steel company. The process features strong asymmetric coupling, large disturbances, and strong nonlinearity. These characteristics are exploited in the following steps to implement intelligent decoupling control. First, three fuzzy expert controllers and two feedforward controllers stabilize the pressure of each gas collector. Then, the three collectors are divided into two groups based on an analysis of the couplings among them to facilitate decoupling control. An intelligent decoupling control method is used to design intragroup and intergroup decoupling controllers. Finally, expert valve control handles the nonlinearity of butterfly valves, and a multirate sampling strategy further improves the control performance. The results of actual runs show that the system satisfactorily performs the intelligent decoupling control of the gas pressures of the coke ovens, sufficiently suppresses disturbances, and accurately stabilizes the pressures.