A one-dimensional Cd(II) chain coordination polymer constructed by an electron-deficient viologen-anchored carboxylate ligand was successfully synthesized. Owing to the favorable stimuli-chromic properties of viologen, the title compound shows reversible photochromism, thermochromism, electrochromism, and naked-eye-detectable differentiable vapochromic response to different volatile amines. The chromic behaviors of it are ascribed to the formation of viologen radicals triggered by external stimuli. And the differentiated response to volatile amines is attributed to the size effect of the amines as well as the steric hindrance effect of forming α/β Cv-H···Namines interactions of the viologen unit to further affect the occurrence of electron transfer. Such an all-in-one crystalline material might have more practical applications in photoelectric, erasable inkless printing, light printing, and volatile amine detection fields.