Detailed studies on Photoluminescence (PL) of porous silicon (PS) with copper deposition were presented. PS was prepared via double electrobath, and then copper was deposited on PS surface by chemical plating. Atomic force microscopy (AFM) measurement indicates that there are different surface morphologies of PS samples with hemispherical, mountain, and tubes-like shape in different etching conditions. PL results show that the PL spectrum intensity of PS with Cu post-deposition increases 50% and do not decay after being laid 4 months than that of PS with pre-deposition. And the peak position from the PL spectrum with Cu deposition has a 14nm blue shift due to the surface stress effect of Cu to PS.