Helical amylose/SWNTs complexes (A/S-C) of various sizes, a single nanotube wrapped by amylose in particular, were demonstrated. The formation process of the helical A/S-C was further explained by a novel hierarchical self-assembly model, including the wrapping of amylose chains around SWNT and the hierarchical self-assembly of wrapped-SWNTs into the superstructural A/S-C. Besides the hydrophobic interaction, the hydrogen bonding also plays a certain role in the self-assembly process.