In this article. we described the synthesis of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups via the free radical polymerization. Oligomers obtained were well characterized by MALDI-TOF-MS, H-1 NMR, FT-IR, UV, CD and SEC. These comb oligomers having macrocyclic pendant groups showed very good solubility in common organic solvents at room temperature. Furthermore, the oligomers could self-assemble into different morphologies by dropping their THF solutions of different concentrations on the surface of water. At a relatively low concentration. the oligomers self-aggregated into hollow spheres. When the concentration was increased, the aggregates changed into solid spheres. The morphologies of the hollow or solid spheres were observed by TEM and ESEM. (c) 2006 Elsevier Ltd. All rights reserved.