Block copolymers composed of a highly isotactic and nonracemic poly(propylene oxide) (PPO) segment joined to a poly(phenylene ethynylene) (PPE) segment, with either meta or para connectivity, were synthesized, and their aggregation and conformational behavior in Solution properties was investigated by optical spectroscopy. Furthermore, graft copolymers based on a in-phenylene ethynylene backbone equipped with isotactic, nonracemic PPO side chains were synthesized and studied with regard to their backbone conformation in Solution. The combination of flexible chiral polymeric segments (PPO) with rather rigid, extended aromatic segments (PPE) promises to be a fruitful concept for generating novel optoelectronic materials with defined levels of intra- and intermolecular organization, i.e., backbone conformation and self-assembly behavior.