This report describes the synthesis and characterization of amphiphilic block-copoly(3-alkylthiophene)s with one hydrophobic and one hydrophilic block. Implementation of a chiral center in one of the two blocks enables a chiroptical evaluation of the materials in different media. Depending on the solvent conditions, phase-separation and selective aggregation of one of both blocks becomes feasible, which has implications on the aggregation behavior of the second block. The presented chiroptical and thermal study provides an insight into the self-assembly of these materials both in solution and in film.