We are investigating applicability of photoacoustic (PA) spectroscopy to porous silicon. Since PA spectroscopy is based on a non-radiative relaxation process, the measurement is of importance as a counterpart to photoluminescent spectroscopy. We studied a dependence of a PA amplitude on a chopping frequency and discussed the influence of a PA signal originated in a silicon substrate. The frequency dependence was elucidated with a two-layer model. Differences in PA spectra are correlated with a photoluminescent efficiency. From the correlation, we believe that non-radiative centers quench the efficiency.