Two methods of synthesis of oligo-6-bromo-6-deoxy-β-cyclodextrins, with use of the Vilsmeier-Haack reagent and via tosyl derivatives of β-cyclodextrin, were compared. The second method holds more promise, since it allows a desired number of bromine atoms to be introduced into the β-cyclodextrin molecule instead of hydroxy groups. A correlation between the decomposition onset points of oligo-6-bromo-6-deoxy-β-cyclodextrins and the number of bromine substituents in them was revealed.