The synthesis of 2-[3,4-bis(n-alkan-1-yloxy)phenyl]-2-oxazolines with alkan = octan, decan, dodecan, and tridecan is presented. Their living cationic ring opening polymerization produces cylindrical macromolecules that self-organize in a hexagonal columnar two-dimensional phase. The structural analysis of these polymers was carried out by a combination of techniques including differential scanning calorimetry, thermal optical polarized microscopy, X-ray diffraction, transmission electron microscopy, electron diffraction, scanning force microscopy, and atomic force microscopy (AFM). The diameter of these cylindrical macromolecules ranges from 33 to 44 Angstrom, and therefore they represent the simplest cylindrical macromolecules that can be directly visualized by AFM on a surface. Preliminary experiments have demonstated the use of these cylindrical macromolecules as models to investigate the creation of two-dimensional and three-dimensional order via direct visualization and thus they represent the simplest nonbiological systems that mimic the role played by the complexes of nucleic acids with proteins in structural analysis by direct visualization.