Porous silicon (PS) of uniform structure was prepared by electroless silver deposition on surface of silicon at near room temperature in HF-AgNO3 system solution. Morphology of PS was characterized by scanning electron microscopy. The results showed that the diameter of hole was 1-2μm and holes distributed regularly. The ethylene diamine tetra acetic acid (EDTA) was an important additive to control the etching rate of silicon, which is of great significance to research the mechanism of porous silicon formation. Furthermore, photoluminescence property of PS was characterized.