The benzoyl-terminated multiarm hyperbranched poly(3-ethyl-3-oxetanethanol) (HBPO-B) was synthesized by reaction of terminal hydroxyl with benzoyl chloride in CH2Cl2 in the presence of pyridine and triethylamine (TEA) as the acceptors of HCl. The macroscopic self-assembly structures of hyperbranched benzoyl-terminated poly(3-ethyl-3-oxetanethanol) can be obtained via a simple solvent volatilizing route and generated multiwalled structures with millimeters in diameter and centimeters in length. Besides the molecular structures. the macroscopic self-assembly of hyperbranched benzoyl-terminated poly(3-ethyl-3-oxetanethanol) is also affected by other factors, such as the nature of the solvent, the molecular concentration, the volatilizing ratio of solvent, and self-assembly temperature. (c) 2005 Elsevier Ltd. All rights reserved.