Nanocrystalline porous silicon surfaces have been used to detect nitroaromatic compounds in vapor phase. The mode of photoluminescence is emphasized as a sensing attitude or detection technique. Quenching of photoluminescence from nanocrystalline porous surfaces as a transduction mode is measured upon the exposure of nitroaromatic compounds. Reversible detection mode for nitroaromatics is, too, observed. To verify the detection afore-mentioned, photoluminescent freshly prepared porous silicons are functionalized with different groups. The mechanism of quenching of photoluminescence is attributed to the electron transfer behaviors of quantum-sized nano-crystallites in the porous silicon matrix to the analytes(nitroaromatics). An attempt has been done to prove that the surface-derivatized photoluminescent porous silicone surfaces can act as versatile substrates for sensing behaviors due to having a large surface area and highly sensitive transduction mode.