Novel photoluminescent Bragg-reflective porous silicon, exhibiting dual optical properties, both the optical reflectivity and photoluminescence, was developed and used for sensing organic vapors. Photoluminescent Bragg-reflective porous silicon samples were prepared by an electrochemical etch of n-type silicon under the illumination. The etching solution consisted of a 3:1 volume mixture of aqueous 48% hydrofluoric acid and absolute ethanol. The typical etch parameters for the generation of photoluminescent Bragg-reflective porous silicon involved a periodic square wave current with 50 repeats. The surface of photoluminescent Bragg-reflective porous silicon was characterized by a FT-IR spectroscopy. Both reflectivity and photoluminescence were simultaneously measured under the exposure of organic vapors. The shift of reflection band to the longer wavelength and the quenching of photoluminescence under the exposure of various organic vapors were observed.