We report on Flory–Huggins photonic sensors for the selective detection of volatile organic compounds without the use of any chemical functionalization. For this purpose, we employed periodic multilayers made of inert cellulose acetate alternated to active polystyrene films whose free volume was modified with silanized ZnO nanoparticles. The simple UV-visible (UV-vis) dynamic optical response of such polymer distributed Bragg reflectors during exposure to vapors of benzene, toluene, o-dichlorobenzene, and carbon tetrachloride allows their detection and recognition based on different chemico–physical affinity with the active polymer medium.