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Currently, selective catalytic reduction (SCR) is one of the main after-treatment systems to control diesel engine NOx emission. But the SCR system is bulky, considering the limited installation space. Therefore, the design of SCR system with the compact structure and reliable performance is one of the essential topics. In this study, the structure parameters, such as catalyst cross-sectional area, catalyst length, substrate wall thickness, coating thickness, channels per square inch (CPSI) of substrate, are taken into consideration to study their effects on the SCR performance and narrow the scope of various structural parameters for the following optimization study. Then, the structural parameters of the SCR reactor are optimized by considering the coupling relationship among these structural parameters by using the Response Surface Methodology (RSM) at high load of diesel engine.