When the organic vapors absorbed to the surface of porous silicon(PS), capillary condensation takes place due to the porous structure of the PS layer, accordingly resulting in the effective refractive index changing. For PS multi-layer microcavities, the different resonant peaks shift in the reflectivity spectrum of porous silicon microcavities(PSMs). The optical sensing model is set up by applying Bruggeman effective medium approximation theory, capillary condensation process and transfer matrix theoretically analytical method of one-dimensional photonic crystals. At the same time, comprehensively researched on are the sensing characteristics of PSMs which are exposed to give concentration organic vapors. At last, made is the theoretical simulation for sensing model of the PSMs in case of saturation by using computer numerical calculation, and found is the linearity relation between the refractive index of organic solvent and the peak-shift. At the same time deduced is the peak-shift as a function of the concentration of ethanol vapors.