The unexpected formation of supramacromolecules of beta-cyclodextrin in aqueous solution under ambient conditions is reported in this article. The shape and size of the supramacromolecules could be controlled by varying the stirring time and the concentration. The supramolecular interactions of the supramacromolecules were confirmed by H-1 NMR spectroscopy. Additionally, visual evidence of the supramacromolecules was provided by transmission and scanning electron microscopy. The thermal behavior of the supramacromolecules was examined by thermogravimetric analysis. The molecular mass determination by gel permeation chromatography showed that the supramacromolecules had a high molar mass.