A series of poly(4-vinylpyridine)-b-poly(ε-caprolactone) (P4VP-PCL) diblock copolymers have been synthesized and used for the formation of nanostructures with tunable colors arising from the association of chromophores with P4VP block in P4VP-PCL. The association of chromophores leads to the bathochromical shifts of charge transfer absorption peaks, resulting in the color appearance into the visible region. To achieve the formation of well-defined nanostructured materials, the phase behavior of the mixtures of chromophore/P4VP-PCL was systematically examined. As evidenced by transmission electron microscopy and small-angle X-ray scattering (SAXS), the phase transformation of self-assembled nanostructures can be easily induced by introducing chromophores due to the association of 2-methylidenepropanedinitrile in the chromophores with the lone-pair electron of nitrogen in P4VP block (that is the increase on the effective volume fraction of P4VP, as identified by SAXS experiments through the analysis of one-dimensional correlation function). As a result, by taking advantage of charge transfer and corresponding morphologies from transformation, well-defined nanostructured films resulting from mixing of chromophore and P4VP-PCL offer the possibility to create stimuli-responsive nanomaterials with tunable color.