Here, we develop a method to fabricate stimuli-responsive color films using block copolymer, poly(4-vinylpyridine)-b-poly(ε-caprolactone) (P4VP-PCL), as a template complexed with functionalized chromophores. The P4VP block in the P4VP-PCL can be associated with a cyano end-capped chromophore via charge transfer, which is a noncovalent interaction that can be conveniently manipulated by external stimuli, giving a specific color. The color of the film can be switched by tuning the charge transfer interaction between the chromophore and P4VP with controlled environmental conditions, such as pH, temperature, and moisture, while maintaining high transmittance for visible light due to the formation of the nanostructure of chromophore/P4VP-PCL complex. However, the association/dissociation process between chromophore and P4VP is diffusion-dominated, which may limit the kinetic response time for color change. A way to create quick and reversible color switching can be achieved by a combination of stimuli. The contrasting color change of the responsive chromophore/P4VP-PCL thin films which exhibit RGB primary colors can provide a sensor film that is flexible, fast-responsive, and convenient.