A porous silicon lm (PS) was investigated by FTIR, Raman and photoluminescence (PL) spectroscopies. The Raman and PL spectra were obtained using four different laser excitations: 488, 514, 633 and 782 nm. The analysis of the first order and second order Raman scattering lines permits to identify the band energy structure of the crystallites inside the PS film. The analysis of PL spectra shows that the intensity and full width at half-maximum values of PL emission depends on intensity and energy of laser excitation. The linear polarization degree (LPD) of the PL spectra also presents a dependence of laser excitation. The observed dependence of Raman and PL spectra due to laser excitation energy cannot be explained within the quantum confinement alone. We propose a mechanism for PL emission in PS layers, in which the radiative recombination occurs in localized centers at pore/crystallite interface. These quasi-molecular centers are Jahn-Teller active.