In this study, various calorimetric and analytical techniques were used to evaluate the thermodynamics of the preparation of adipic acid through the oxidation with hydrogen peroxide. The reaction exotherm was combined with the reaction mechanism. Differential scanning calorimetry revealed that the hydrogen peroxide was relatively stable when Na2WO4.2H2O and H2SO4 were used as cocatalysts. Reaction calorimetry, in situ Fourier transform infrared spectroscopy and gas chromatography/mass spectrometry (GC/MS) results indicated a possible macroscopic reaction pathway at 73 and 90°C stage. Furthermore, the results obtained through adiabatic calorimeter (Phi‐TEC II) and GC/MS indicated the possibility of catastrophic accidents if control of the target reaction was lost. The criticality classes of this reaction were of Grade 5. The results of this study can be further used to improve the inherent safety of its operating measures, as a result, this reaction process can be scaled up.