In this article, we report the self-assembly of flocculation- resistant multimolecular micelles with thermoresponsive corona from novel dendritic heteroarm star copolymers. The micelles have a core-shell-corona structure at room temperature according to pyrene probe fluorescence spectrometry, proton nuclear magnetic resonance (H-1 NMR), transmission electron microscopy, and dynamic light scattering measurements. Increasing the temperature above the lower critical solution temperature (LCST), the micelles show high flocculation-resistant ability resulting from a structure transition from core-shell-corona to core-shell confirmed by a quantitative variable temperature H-1 NMR analysis method using potassium hydrogen phthalate as an external standard. A big volume change of the micelles is observed during the LCST transition. The drug loading and temperature-dependent release properties of the micelles are also investigated by using coumarin 102 as a model drug, which displays a rapid drug release at a temperature above the LCST. (C) 2010 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem 48: 4428-4438, 2010