Multi-walled carbon nanotubes (MWCNTs) have remarkable properties. However, their thermal stability characteristics, which may represent potential hazards during the production or utilization stage, concern unsafe or unknown properties researches. Our aim was to analyze the thermokinetic parameters of different heating rates by differential scanning calorimetry (DSC) and thermogravimetric analyzer (TG), and then to compare thermal decomposition energy parameters under various conditions by well-known kinetic equations. MWCNTs were acidified via nitric acid (HNO3) in various concentrations from 3 to 15 N and were characterized by means of Fourier transform infrared (FTIR) spectrometry. For original and modified MWCNTs, we further identified the thermal degradation characteristics of the functional group by TG-FTIR. Finally, we established an effective and prompt procedure for receiving information on thermal decomposition characteristics and reaction hazard of MWCNTs that could be applied as an inherently safer design during normal or upset operation.