Rod-coil copolymers with an oligomeric rod aggregate on a nanometer length scale, which is important for many applications like e.g. organic photovoltaics. However, this aggregation behavior and the driving forces such as hydrogen bonding and pi-pi interactions, as well as the role of side groups, are not yet fully understood. Here, we investigated these noncovalent interactions in oligo(p-benzamide) poly(ethylene glycol) (OPBA-PEG) copolymers using solid-state NMR supported by wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC). and polarization optical microscopy (POM). It was found that longer OPBAs form layered beta-sheet-like aggregates and that these are stabilized by amide hydrogen bonds in both unsubstituted OPBAs and OPBA-PEG rod-coil copolymers. The binding of the PEG also introduces a liquid crystalline phase. As a consequence, the local structural order is improved in the copolymer. Thus, by combining different methods of structural investigation, we were able to develop a model of local aggregation and packing in both the liquid crystalline and the solid state.