Smart chromic materials reacting to physicochemical stimuli are widely applied in optical switches, smart windows, and chemical sensors. Currently, most materials only respond to a single stimulus, but those that respond to multiple external stimuli are still in the minority. Herein, we report a novel porous zinc tungstate@metaloxoviologen framework [Zn3(Bcbpy)6(H2O)2]-[ZnW12O40]·6H2O (ZnW12@MV, H2BcbpyCl2 = 1,1′-bis(3-carboxybenzyl)-4,4′-bipyridinium dichloride), which shows multiple stimulus-responsive properties due to a combination of different functional motifs, namely, viologen electron acceptors, luminescent zinc–oxygen-clusters, porous cationic frameworks, and ZnW12O406− electron donors. Generally, the large-sized polyoxometalate (POM) anions serving as structure-directing agents can easily direct the formation of the oligomeric metaloxoviologen cations, mainly because POMs may break down some linkages leaving larger spaces for themselves. The large ZnW12O406− anions in ZnW12@MV are encapsulated into three-dimensional (3D) metaloxoviologen frameworks built up from the linkages of trinuclear zinc–oxygen clusters and Bcbpy viologens, which offer the first example of a 3D metaloxoviologen framework induced by large-sized POM anions. ZnW12@MV shows a reversible chromic response to X-ray/UV and electricity via different stimulus-induced electron transfers between electron-rich POM anions and electron-deficient metaloxoviologen frameworks, whereas the coloration changes are ascribed to the formation of radical and mixed-valence colored state ZnW12O406− species. The photochromic behavior is accompanied by photoluminescence quenching. The discriminative response to different-sized amines is attributed to the formation of viologen radicals through host–guest electron transfer. These results indicate that the multi-stimulus response ZnW12@MV can be applied in electrochromic devices, inkless erasable printing, and the detection of amines. [ABSTRACT FROM AUTHOR]