An efficient synthesis of the title compound, per-6-bromo-per-2,3-dimethylβ-cyclodextrin, is described, giving access to a highly soluble cyclodextrin, which may be used for further chemical modification of β-cyclodextrin. Crystals of the target compound were grown and the solid state structure was determined by X-ray crystallography, revealing a cyclodextrin derivative whose conformation deviates substantially from C7 symmetry.