A new selective catalytic reduction (SCR) system for captive power plants in the petrochemical industry was analyzed. The key components suitable for the target SCR system were obtained using computational fluid dynamics (CFD) numerical simulation combined with a cold physical model. The structural characteristics of the SCR system were studied, and corresponding design schemes were obtained for the key components, such as the guide plate, the ammonia injection grid (AIG), the static mixer, and the rectifier grille. The distributions of the flue gas velocity and the NH3 concentration within the flue cross-section in front of the first layer catalyst were studied in detail. Synchronously, the pressure loss and the temperature reduction characteristics in the SCR system were also considered. CFD results showed that the average standard deviation of the flue gas velocity was about 11.61%, and the average standard deviation of the NH3 concentration distribution could reach about 3.79% under the five operating conditions. It could be concluded that the uniformity of the flue gas velocity and the NH3 concentration distribution within the above flue cross-section was guaranteed by comparing to the design standard of 15% and 5%, respectively. It was further found that the maximum pressure loss between the inlet and the first layer catalyst was about 106.64 Pa, and the temperature reduction characteristic of the entire SCR system could be maintained within ±0.01 °C, which indicated that no extreme adverse effect arose due to the introduce of the key components. The cold physical model experiment was accordingly conducted to verify the reliability of the above CFD results. The cold physical model experiment results showed that the average standard deviation of flue gas velocity was about 8.82%, and the average standard deviation of NH3 concentration distribution could reach about 4.21%. The maximum biases for the standard deviations of the flue gas velocity and the NH3 concentration distribution were approximately 4.83% and 1.18% under the five operating conditions. Based on the good agreement of the research results via the two different methods, the designed key components of a new SCR system could be confirmed to be feasible, which would benefit the deNOx performance of the SCR system.