The synthesis and characterization of a novel class of structurally well-defined nanotubes from β-cyclodextrin are described. These new hosts were formed using disulfide linkages that substitute all the primary hydroxyl groups of a β-cyclodextrin. A deep and rigid hydrophobic channel with a size of more than 1.5 nm is found in the molecules. Because of their unique geometry and the potential biodegradability of the disulfide bond, this class of molecules could find broad applications in biology and other areas of research.