A new supramolecular self-assembly approach to construct micelles and reverse micelles was reported. Double-hydrophilic block copolymers poly(ethylene oxide)-b-poly(N-isopropylacrylamide) (PEO-b-PNIPAAm) was synthesized via atom transfer radical polymerization (ATRP) using PEO macroinitiator. Because of the lower critical solution temperature (LCST) phase behavior of PNIPAAm, PEO-b-PNIPAAm block copolymers self-assembled to form PNIPAAm-core micelles at 40°C. The PNIPAAm-core micelles were disassembled to unimers when the temperature was decreased to 25°C. But the addition of α-cyclodextrins (α-CDs) could induce the formation of PNIPAAm-shell micelles because of the "channel-type" crystallities induced by PEO/α-CDs polyrotaxanes. The assembly and disassembly procedure of micelles and reverse micelles were investigated by dynamic light scattering (DLS), X-ray diffraction (XRD), 1H NMR and transmission electron microscopy (TEM).