In this study, X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry (DSC) method were used to analyze the main characteristics of sweet potato starch, and to analyze the thermal degradation process of sweet potato starch. Specifically, X-ray diffraction to study its structure, thermogravimetric analysis to study the thermal degradation kinetics, and differential scanning calorimetry to study the thermogram of sweet potato starch. The thermal decomposition kinetics of sweet potato starch was examined within different heating rates in nitrogen atmosphere. Different models of kinetic analysis were used to calculate the activation energies using thermogravimetric data of the thermal degradation process. Activation energies obtained from Kissinger, Flynn-WallOzawa, and Šatava-Šesták models were 173.85, 174.87 and 174.34 kJ/mol, respectively. The values of activation energy indicated that the thermal degradation of the sweet potato starch was a single reaction mechanism or the combination of multi-reaction mechanisms. The differential scanning calorimetry analysis show that two decomposition stages were presented: the first at a low temperature involves the decomposition of long chain; and the second at a high temperature represents the scission of glucose ring. This information was helpful to design the processing process of many natural polymers. Thermogravimetric Fourier transform-infrared (TG–FTIR) analysis showed that the main pyrolysis products included water, methane, carbon dioxide, ammonia, and others.