The influence of electron-phonon coupling in the emission spectra of self-assembly (SA) films of poly(p-phenylene vinylene) (PPV) is discussed. PPV is an important polymeric system because it exhibits strong luminescence effect. A semi-empirical model was used to analyze the photoluminescence spectra of PPV. This model assumes that defects along the molecule give rise to a distribution of conjugated segments of different lengths. In addition, it was considered that electronic transition was essentially coupled with three effective phonon modes with correspondent energies at 62, -139 and 192 meV, which were observed experimentally.