Pyrene was inserted into a low-density polyethylene matrix. Fluorescence spectra as a function of temperature and the differential scanning calorimetry (DSC) trace were recorded simultaneously. Along with the usual vibronic bands, a low-intensity band at 365 nm appears at higher energies with respect to the 0-0 transition in the pyrene fluorescence spectra. The fluorescence intensity of this small band increased with temperature, and an isoemissive point was observed to occur at 368 nm. This emission was interpreted as arising from pyrene molecules located in the outer rigid interfacial region of polymer crystallites. Its temperature-dependent fluorescence was interpreted in terms of electron-phonon coupling; two phonons which coincide with fundamental vibrations of polyethylene were necessary to fit experimental data. Coupling with a high-energy phonon was possible at low temperature, whereas, above the beta relaxation temperature, phonon coupling occurs with a lower-energy phonon. The a relaxation was detected as a maximum in fluorescence intensity since above its characteristic temperature, nonradiative processes begin to operate.