We studied the effect of temperature on electron-phonon coupling in the emission spectra of poly(p-phenylene vinylene), PPV, prepared by self-assembly methodology. Site selective luminescence spectroscopy (SSE) was employed to resolve the fine structures of the vibracional modes. Using Franck-Condon analysis, the experimental vibronic progressions of PPV can be well described by three effective, inhomogeneous broadened vibrational modes with energies at 330, 1163 and 1550 cm(-1). As the temperature increases the electron-phonon coupling for the 1550 cm(-1) mode remains constant while, for the other two modes, the S factor increases.