An　efficient　photocatalyst　based　on　the　broadband　solar　response　molecular　system　was　designed　and　constructed　for　pollutant　degradation　in　near-neutral　conditions　via　utilizing　guest　polyoxometalate　cluster　sensitized　with　electron　deficient　host　network.　Photoelectrochemical　analysis　reveals　electron-hole　pairs　are　generated　efficiently　upon　both　visible　and　NIR　light　excitation.　Its　photocatalytic　activity　in　the　visible　and　NIR　light　regions　is　enhanced　because　of　the　contribution　from　the　broad　absorption　of　copper-viologen　framework　and　the　strong　host-guest　interactions.　This　stable　heterogeneous　catalyst　is　easily　recollected　and　regenerated　without　the　loss　of　activity　for　the　next　cycle.　©　2018　American　Chemical　Society.