Several poly(ionic liquid)s (PILs) were synthesized and assembled with a multielectronic-process sustaining polyoxometalate (POM) into new green and water-insoluble nanomaterials (POM@PILs). They are visible light photosensitive, unlike their two components. A synergic effect was highlighted for the first time. POM@PILs achieve complete photodegradation of AO7 in aerobic media. The photocatalysts were recoverable and recyclable.