A series of amphiphilic aromatic hyperbranched polyesters (HBPEs) were firstly synthesized by way of polycondensation with 1,2,4-benzenetricarboxylic anhydride (BTAA) and polyethylene glycol (PEG300, PEG400, PEG600). Structure and property of HBPEs were characterized by FT-IR, H-1 NMR, GPC, DSC and TGA. The obtained HBPEs have a good thermal stability and can self-assemble into vesicles in water. These vesicles might be applied as microreactors or drug carriers etc.