On the basis of terminal group electrostatic interactions (TGEI), a supra-amphiphile is formed between a homopolymer of polylactic acid with carboxyl group at one end (PLA-COOH) and hepta-6-hydrazyl-beta-cyclodextrin (HH-CD). The amphiphile can self-assemble into a micellar structure in aqueous solution. The outer surface of the micelle, which is composed of cyclodextrins, can be further modified via host guest interactions. Considering the biocompatibility of the building blocks, the application of the micelles in a nanocarrier of anticancer drugs is further explored.