In this paper, the well-defined amphiphilic diblock copolymers, hyperbranched polyethylene-b-poly(ethylene oxide) (HBPE-b-PEO) and hyperbranched polyethylene-b-poly(acrylic acid) (HBPE-b-PAA), were synthesized by combing chain walking ethylene polymerization in the presence of 4-vinylbenzyl chloride catalyzed with Pd-alpha-diimine and click chemistry or atom transfer radical polymerization (ATRP). The self-assembly behavior in water, a selective solvent for PEO and FAA, and the micelle morphology of HBPE-b-PEO and HBPE-b-PAA were investigated by laser light scattering (LLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The resultant diblock copolymers can self-assemble into spherical vesicles as demonstrated by LLS and TEM, which become collapsed on mica surface during drying as showed by AFM. (C) 2014 Elsevier Ltd. All rights reserved.