Exciton migration! Spectroscopic analyses and extensive molecular dynamics studies revealed a well‐defined 41 helix in which the perylene molecules (see figure) form four “helter‐skelter‐like” overlapping pathways along which excitons and electrons can rapidly migrate. We report on a combined experimental and computational investigation on the synthesis and thorough characterization of the structure of perylene‐functionalized polyisocyanides. Spectroscopic analyses and extensive molecular dynamics studies revealed a well defined 41 helix in which the perylene molecules form four “helter skelter‐like” overlapping pathways along which excitons and electrons can rapidly migrate. The well‐defined polymer scaffold stabilized by hydrogen bonding, to which the chromophores are attached, accounts for the precise architectural definition, and molecular stiffness observed for these molecules. Molecular …