We have used a long chain dodecylbenzenesulfonate ion (DBS) to produce self-assembled multilayer structures of poly(p-phenylene vinylene) (PPV) with special features. Rather than alternating layers provided of a PPV-precursor (the poly(xylylidene tetrahydrothiophenium chloride or PTHT) and a polyanion, the alternated adsorption process was carried out with the PPV-precursor and the DBS ions in aqueous solution. The internal layer structure of these PTHT- DBS films is therefore different from conventional layer-by-layer films, since DBS is expected to be incorporated into the PTHT chain via counterion exchange. As a consequence, the conjugation length could also be controlled by controlling the DBS content in the film. Further advantage of introducing DBS lies in the possibility of converting films with a high conjugation length at 115 oC within only 3 min. The luminescence and absorption spectra at low temperatures show a very intense well-resolved vibronic structure. We also demonstrated the band-gap control of PPV films with a possible heterostructure formation.