Detailed kinetic analysis of Cassava starch thermo-oxidative degradation was performed, using thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG) at four different heating rates. It was found that degradation process is very complex, as identified through continuous change of apparent activation energy with degree of degradation. It was established that process proceeds through three main degradation stages with one additional sub-stage attached to the second degradation stage, which was detected by appearance of “shoulder” on DTG curves. It was found that most important degradation stage can be described by “lumped” model, which implies that free radicals simultaneously attack both linear and branched molecular forms of the starch. This is characterized by an unusually high value of obtained reaction order (n = 3.49). Application of nonlinear least squares method was confirmed the reliability of evaluated kinetic parameters and function of reaction mechanism, which were derived on the basis of other kinetic methods.