The current emission regulations, US Tier-4 and EU Stage-V, are only able to satisfy the regulations when all currently mass-produced emission reduction technologies such as EGR, DOC, DPF, and SCR are applied. Therefore, in this study, for the application of the Urea-SCR system to non-road diesel engines, the database was established by measuring the NO, NO2 concentration and calculating the NO2/NOx ratio based on the catalyst temperature and exhaust mass flow rate. Also, based on the measured NO2/NOx ratio data, a mathematical model was proposed to predict the NO2/NOx ratio at SCR catalyst, and the suitability of the model was verified through steady-state and transient mode. As a result of comparing the NO2/NOx ratio measured at the DOC outlet under the steady-state condition to two model values separately, the R2 was 0.9811 for the 3D map model and 0.9303 for the mathematical model. And in the case of the NO2/NOx ratio measured at the DPF outlet, the R2 was 0.9797 for the 3D map model and 0.935 for the mathematical model. It was confirmed that the R2 with the model value of the 3D Map of the mathematical model in the transient mode is 0.957, which shows high reliability.