Silicon nanowires (SiNWs) were fabricated by a metal-assisted chemical etching of Si and the porous structure on their surfaces was controlled by changing the volume ratio of the etching solution composed of hydrofluoric acid, hydrogen peroxide, and deionized water. The concentration of hydrogen peroxide as the oxidant was varied for controlling the porosity of SiNWs. The optical properties of porous SiNWs were unique and very different from those of single-crystalline Si, as characterized by measuring their photoluminescence and Raman spectra for different porosities.