In the present work, the oxidized corn starch was prepared by using chlorine dioxide as novel oxidant. It was characterized by X-ray diffraction, scanning electron microscope (SEM), and transmission electron microscope (TEM). The main factors that affect the oxidation process were studied, and the oxidation degree of oxidized starch was determined by the carboxyl content and viscosity of the product. The results show that carboxyl groups are introduced into the starch chains successfully, and the oxidation reaction mainly carries out at the amorphous area. Compared with native starch, the light transmittance and anti-retrogradation of oxidized starch increase, whereas the viscosity reduces. The best oxidized starch can be obtained at the sodium chlorate dosage of 3%, hydrochloric acid 4%, and sulfuric acid 3% (all based on the initial starch weight), while the oxidation reaction is conducted at 50°C for 5 h.