A new porous silicon (PSi) microcavity sensor for the detection of volatile organic compounds (VOCs) was developed. PSi microcavity sensor exhibiting unique reflectivity was successfully obtained by an electrochemical etching of silicon wafer. When PSi was fabricated into a structure consisting of two high reflectivity muktilayer mirrors separated by an active layer, a microcavity was formed. This PSi microcavity is very sensitive structures. Reflection spectrum of PSi microcavity indicated that the full-width at half-maximum (FWHM) was of 10 nm and much narrower than that of fluorescent organic molecules or quantum dot. The detection of volatile organic compounds (VOCs) using PSi microcavity was achieved. When the vapor of VOCs condensed in the nanopores, the refractive indices of entire particle increased. When PSi microcavity was exposed to acetone, ether, and toluene, PSi microcavity in reflectivity was red shifted by 28 nm, 33 nm, and 20 nm for 2 sec, respectively.