Liver glycogen (involved in maintaining blood-sugar levels) is a hyperbranched glucose polymer containing β particles (diameter ~20 nm), which can form composite α particles (diameter ~50-300 nm), and includes a small but significant amount of bound protein. Size distributions of glycogen from livers of healthy and diabetic mice were examined using size-exclusion chromatography with two separate eluents: aqueous eluent and dimethylsulfoxide (DMSO) eluent. Morphologies were examined with transmission electron microscopy. Diabetic glycogen (DG) exhibited many α particles in the mild water-based solvent, but in DMSO, which breaks H bonds, these degraded to β particles; α particles however were always present in healthy glycogen (HG). This DG fragility shows the binding of β into α particles is different in HG and DG. The diabetic α particle fragility may be involved with the uncontrolled blood-sugar release symptomatic of diabetes: small β particles degrade more easily to glucose than α particles. This has implications for diabetes management.