An effective strategy to synthesize multifunctional materials is the incorporation of functional organic moieties and metal oxide clusters via self-assembly. A rare multifunctional radical-doped zinc-based host guest crystalline material was synthesized with a fast-responsive reversible ultraviolet visible light photochromism, photocontrolled tunable luminescence, and highly selective photocatalytic oxidation of benzylic alcohols as a result of blending of distinctively different functional components, naphthalenediimide tectons, and polyoxometalates (POMs). It is highly unique to link pi-zelectron-deficient organic tectons and POMs by unusual POMs anion-pi interactions, which are not only conducive to keeping the independence of each component but also effectively promoting the charge transfer or exchange among the components to realize the fast-responsive photochromism, photocontrolled tunable luminescence, and photocatalytic activity.