The assembly behavior at surfaces of very stiff polyisocyanopeptides (PICs) functionalized with semiconducting perylenebis(dicarboximide) (PDI) side chains has been investigated by atomic force microscopy. These multi-chromophoric arrays are unique as they combine an ultra-stiff central polymer main-chain scaffold upon which the PDI chromophores can self-organize through π–π stacking, making them interesting and versatile building blocks for nanoelectronics. In this paper we compare three PIC derivatives featuring different side groups: M1—no chromophores, M2—chromophores capable of π–π stacking, and M3—chromophores where the stacking is hindered by the presence of bulky substituents in the bay area of the PDI. The effect of the different side functionalizations on the macromolecule assembly at surfaces was compared by studying the morphology and aggregation tendency of all three polymers …