Structural colors are formed by the periodic repetition of nanostructures in a material. Upon reversibly tuning the size or optical properties of the repetitive unit inside a nanostructured material, responsive materials can be made that change color due to external stimuli. This paper presents a simple method to obtain films of ethanol vapor-responsive structural colors based on stacked poly(N-isopropylacrylamide) (PNIPAM)grafted silica nanoparticles. Our materials show clear, reversible color transitions in the presence of near-saturated ethanol vapor. Moreover, due to the absorption of ethanol in the PNIPAM brushes, relatively long recovery times are observed (∼30 s). Materials based on bare or poly(methyl methacrylate) (PMMA) brush-grafted silica nanoparticles also change color in the presence of ethanol vapor but possess significantly shorter recovery times (∼1 s). Atomic force microscopy reveals that the delayed recovery originates from the ability of PNIPAM brushes to swell in ethanol vapor. This renders the films highly suitable for ex situ ethanol vapor sensing.