Self-assembly films of poly(p-phenylene vinylene) (PPV) were prepared by dipping quartz substrates alternately in solutions of the PPV polymer precursor poly(xylylidene tetrahydrothiophenium chloride) (PPV-precursor) and of a sodium salt of dodecylbenzenesulfonic (DBS) acid. The advantage of introducing DBS lies in the possibility of converting films with a high conjugation length at 115 T within only 3 min. By controlling the DBS concentration, symmetrical and non-symmetrical PPV heterostuctures can be realized with a macromolecular manipulation during the dipping direction, leading to enhanced optical proprieties.