The paper presents the results of the common project performed with the Federal Institute for Materials Research and Testing, Berlin, Germany (BAM) concerning the comparison of the experimental results with simulations based on the application of the kinetic-based method and heat balance of the system for the determination of the self accelerating decomposition temperature (SADT). The substantial potential of the kinetic-based method is illustrated by the results of the simulation of SADT of azobisisobutyronitrile (AIBN). The influence of sample mass and overall heat transfer coefficient on the SADT values were simulated and discussed. Simulated SADT values were verified experimentally with a series of large-scale experiments (UN test H.1 [1]) performed with packaging of 5, 20 and 50 kg of AIBN in an oven at constant temperatures. Additionally, the results of small-scale test H.4 for SADT determination based on the heat loss similarity as described in details in the UN Manual [1] were compared with the simulated data based on kinetic approach. The paper presents also the basic principles of a new kinetic analysis workflow in which the heat flow traces (e.g., DSC) are simultaneously considered with results of large-scale tests as e.g., H.1 or H.4. Application of the newly proposed kinetic workflow may increase accuracy of simulations of SADT based on results collected in the mg-scale and considerably decrease the amount of expensive and time consuming experiments in kg-scale tests.