In the present paper, we have not only investigated the top surface and cross-section morphology, but also measured photoluminescence spectra characteristic of porous silicon after deposition of metallic ions by electrochemical deposition employing scanning electron microscopy (SEM) and spectrometer, respectively. It is apparent from the SEM images that the microstructure of porous silicon is seriously ruined by the metallic ions deposited by electrochemical deposition. Most interesting is the finding that in the photoluminescence spectrum of porous silicon after the deposition of metallic ions such as AL3+ and Cu2+, the luminescence band gradually is quenched as the electrochemical deposition progressed. A careful consideration of the results obtained show that according to the basic theory of well-established quantum confinement model, the quenching of photoluminescence spectra of porous silicon may well be attributed to the microstructure fell into ruin. On the other side of the fence, we can interpret the physical origin of the phenomenon in view of the presence of metallic ions which give rise a series of energy level deep in the band gap of porous silicon.