A　photocatalytic　active　phosphotungstate　cluster　is　incorporated　into　the　backbone　of　an　electron-deficient　copper-viologen　framework　via　a　copper-substituted　and　coordination　connection.　Self-assembly　with　a　bottom-up　designed　strategy　allows　functional　units　to　be　organized　into　an　ordered　arrangement　[Cu2(H2O)3(CPBPY)2(CuHPW11O39)]·7H2O　(1)　that　tunes　the　band　structure　and　engineers　the　optical　energy　gap　of　the　photocatalyst.　Interactions　between　the　electron-deficient　host　framework　and　the　captured　guest　cluster　strengthens　the　photogenerated　electron-hole　separation.　This　designed　catalytic　molecular　system　shows　a　high　photooxidation　capability　toward　the　degradation　of　dye　pollutants　with　a　UV,　visible,　and　even　near-infrared　light　response.　Copyright　©　2019　American　Chemical　Society.