In this work, we study on the formation of Au nanoparticles separately on fresh and oxided porous silicon microcavity substrates. The fabrication of Au/PSM is simple, rapid, flexible and easy to be controlled. The amount of AuNPs deposited on fresh PSM substrates is much more than that of AuNPs deposited on oxided PSM substrates. And AuNPs are easy to be deposited on fresh PSM substrates. AuNPs deposited on fresh PSM substrate provide an interesting way in diverse areas of electronics, optics, material research, and medical science.