Summary: A chiral, regioregular poly[3‐(4‐alkoxyphenyl)thiophene] has been prepared and studied. Films prepared by fast evaporation of the solvent, consist of random‐coils, while films prepared by slow evaporation are composed of chirally aggregated, coplanar strands. Heat treatment transforms the random‐coils into aggregated films via an intermediate state, which was characterized as chiral, coplanar, unaggregated polymer strands.