In this article, we report on the observations that in the aqueous electrolyte of aluminum nitrate, the thin metallic conducting films on both internal and external surface of porous silicon (PS) thin films that emit visible photoluminescence at room temperature prior to electrochemical deposition have been obtained under electrochemical deposition condition. Add to this high surface-to-volume ratio and these make it a good candidate for the catalyst supporter. We have investigated the surface morphology of PS after the interval of about 30 hours of electrochemically deposited aluminum by means of scanning electron microscopy (SEM). It has been shown from SEM images that not only micrometer-sized pores are smoothed by deposition of aluminum microcrystal, but also the presences of semi-sphere aluminum microcrystal which rooted in the tip of micrometer-sized pores are observed. On the one hand, this extremely interesting phenomenon which the micrometer-sized pores are smoothed may be explained in terms of principle of electrochemical deposition; on the other hand, we have laid the formation mechanism of semi-spherical aluminum microcrystal at the door of Gibbs free energy.