This study reports a comparative analysis on time dependent degradation of photoluminescence (PL) spectra of porous silicon (PS) during dark-aging (DA) and photo-aging (PA). Fourier Transform Infrared (FTIR) spectroscopy studies have been performed to get an insight on possible chemical changes in the PS surface. It has been found that SiHx bonds decrease progressively while SiOx bonds increase. FTIR and PL measurements revealed presence of blue shifts in the PL spectra during the aging stages (PA and DA). While the PL intensity of dark aged PS shows a decrease during the first 3 weeks and an increase afterwards, the PL intensity decreases continuously for photo-aged PS. The change in the PL spectra has been investigated by overlapping of two different PL bands which are reflective of oxidation of PS surface and size of Si naonocrystallites. A possible bond configuration model about the oxidation of PS surface has also been proposed. The results are interpreted in terms of quantum size effects in PS and the influence of the surface composition. (c) 2010 Elsevier B.V. All rights reserved.