A series of helix-coil diblock copolymers based on poly(ethylene oxide) and optically active helical poly[ {(+)-2,5-bis [4'-((S)-2-methylbutoxy)phenyl] styrene] (PMBPS) were synthesized via atom transfer radical polymerization (ATRP). The synthetic methodology permitted straightforward preparation of the diblock copolymers with relatively low polydispersities and a broad range of compositions and molecular weights. Depending on the composing block length and the initial concentration, the copolymers self-assembled into different supramolecular structures in aqueous solution, including spherical micelles, vesicles, multilamellar vesicles, large compound vesicles, and tubules.