The synthesis and self‐assembly of novel semiconducting rod–coil type graft block copolymers based on poly(para‐phenylene vinylene) (PPV) copolymers is presented, focusing on the ordering effect of linear versus hyperbranched side chains. Using an additional reactive ester block, highly polar, linear poly(ethylene glycol), and hyperbranched polyglycerol side chains are attached in a grafting‐to approach. Remarkably, the resulting novel semiconducting graft copolymers with polyether side chains show different solubility and side‐chain directed self‐assembly behavior in various solvents, e.g., cylindrical or spherical superstructures in the size range of 10 to 120 nm, as shown by TEM. By adjusting the molecular weight and the topology of the polyether segments, self‐assembly into defined superstructures can be achieved, which is important for the efficient charge transport in potential electronic applications.
