Mw value of the chains of the polysaccharide molecules eluted from the sample of DO 1.5 % (DAS1-5, 2.2×106) was by one order lower than the average molecular weight of native starch molecules (30×106). Even more significant decrease in molecular weight up to 6.4×104 was observed for the DAS5 sample. The chain length distribution of amylopectin structural units of native and DAS was characterized by the hydrolysis with isoamylase followed by treatment with β-amylase. Chain distribution profiles of completely debranched samples were available from a high-pressure size exclusion chromatography with multiangle laser light scattering and refractometric index detectors. The oxidation slightly changed the average molecular weight (Mw) of the A-type chains although it evoked changes in the mass ratio of the A-type chains. The weight average molecular weight Mw and mass ratio of B-type chains significantly differed depending on DO of the sample. X-ray diffraction patterns indicated that crystallinity of DAS1-5 and DAS5 decreased in relation to native starch. Oxidised starches of the highest DO were fully amorphous.