The electrochemical deposition technique was applied to achieve porous silicon (PS) surface passivated with Ag deposition for improving the properties of PS photoluminescence. The relation of Ag depositing forms to current density and the effect of PS hydrophilic surface on deposition uniformity were investigated. The experimental results indicated that there were two critical current densities (maximum and minimum) in which Ag was absent and electroplated on PS surface correspondingly, and the range of current density for deposition of Ag on porous silicon was from 50 μA/cm^2 to 400 μA/cm^2. The process of changing PS surface from hydrophobic into hydrophilic had positive effect on Ag deposition uniformity. Under the same experimental conditions, PS hydrophobic surface presented uneven Ag deposition.However, hydrophilic surface treated with SC-1 solution was even. Finally, the effect of PS surface passivation with Ag even deposition on photoluminescence intensity and stabilization of PS was studied. It was discovered that Ag passivation inhibited the degradation of PL intensity effectively. In addition, excessive Ag deposition had a quenching effect on room-temperature visible photoluminescence of PS.