Highly fluorescent bilayer-walled and monolayer-walled nanotubes are assembled from elaborately designed asymmetric perylene diimide (PDI) molecules. The diameter of bilayer-walled nanotubes increases with the size of the branched substituents at the meta-position of the phenyl moiety of PDI molecules, whereas that of monolayer-walled nanotubes remains unchanged regardless of the size of branched substituents.