The synthesis and self-assembly of a comb oligomer having rigid racemic binaphthyl macrocyclic pendant groups are described. The coupling of two structural motifs at the molecular level, e.g., a nanometer-size chiral cavity, and a flexible polymeric backbone, could lead to new opportunities in molecular recognition and separation. The macrocyclic monomers were synthesized followed by introduction of an acrylate side-group, and through free-radical polymerization, they yielded a comb oligomer. Most importantly, this novel oligomer can self-assemble into solid or hollow spheres when tetrahydrofuran (THF) solutions of the oligomer at different concentrations are dropped onto the surface of water. The morphology of the solid or hollow spheres was observed by TEM, ESEM and DLS.