In order to meet the increasing pollutants discharge standard, the selective catalytic reduction (SCR) module in the diesel engine after-treatment system is an important means to reduce nitrogen oxide (NOx) emissions. SCR systems are prone to urea crystallization at lower temperatures, especially during the cold-start conditions of diesel engines. In this study, we use the diesel engine after-treatment system test bench to obtain the boundary parameter of the simulation modules, and the urea crystallization risk assessment model of the diesel SCR system is established. Comparing the computational fluid dynamics (CFD) results with the test bench results, it is shown that the predicted urea film distribution of the assessment model is in good agreement with the experimental results. In order to clarify the various factors that affect the urea crystallization risk, this paper conducts a simulation analysis on a nozzle and mixer structure and operating parameters. The CFD results indicate that the increase in urea spray time will increase the maximum urea film thickness on the SCR system mixer surface. Exhaust temperature is the most important influencing factor. When the diesel engine exhaust temperature increases from 190 °C to 300 °C, the maximum urea film thickness decreases by 32 and the urea film mass accumulation decreases by 5%. Exhaust flow has a small impact on urea crystallization risk. When the exhaust flow increases from 300 kg/h to 600 kg/h, the maximum urea film thickness decreases by 39% and the urea film mass accumulation decreases by about 1%. In addition, urea spray rate, nozzle numbers, spray angle, and spray cone angle are also factors that affect urea crystallization risk.