Starch degradation often coincides with its chemical modification, and understanding how chemical modification influences starch degradation is vital for determining the properties of the resultant modified products. This work investigates the effect of oxidation on starch molecular degradation, examining factors such as oxidation degree, reaction kinetics, and degradation patterns during 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated starch oxidation under varying conditions, including reaction time, pH, temperature, and concentrations of NaBr, TEMPO, and NaClO. Results emphasize that extended reaction durations primarily lead to β-elimination, causing α-1,4 linkage cleavages. pH 8.5 favored non-selective oxidation, while pH 11 enhanced β-elimination, both slowing the reaction rate and severely damaging starch chains (M