We report a set of coiled-coil peptides, radially functionalized with bipyridines, that demonstrate hierarchical assembly into banded rectangular nano- and microstructures, the dimensions of which vary with the strategic placement and number of aromatic groups on the monomer backbone. Finer structural aspects of the hexagonal packing of the individual trimers were determined by X-ray scattering, including intertrimer aromatic interactions between bipyridine moieties. The ease of formation of these biomaterials under physiological conditions and the use of pH to reversibly modulate assembly demonstrate future potential for a range of biological applications, such as drug delivery in a pH-controlled manner.