Spinel ferrite materials have an electronic band structure that is well suited for visible light-induced catalysis, however, their photocatalytic activity remains low due to the daunting charge-carrier separation process. In this article, we report that high-surface-area mesoscopic architectures composed of tightly connected ultrasmall spinel ferrite nanocrystals can efficiently suppress electron-hole recombination, manifesting an exceptional activity and magnetic recyclability in photocatalytic reduction of aqueous Cr(VI). Revealed by electron microscopy, N-2 physisorption, and X-ray scattering studies, the resulting materials, which were obtained through a block copolymer-assisted cross-linking aggregation of colloidal nanoparticles, show a 3D interconnected nano porous structure with a large internal surface area (up to 159 m(2) g(-1)) and exhibit small grain composition (ca. 6-8 nm in size). Through a systematic synthesis of various structural analogues to the spinel ferrite family and optical absorption and electrochemical impedance spectroscopy analyses, we demonstrate that the electronic band structure fits the electronic requirements for both Cr(VI) reduction and water oxidation under UV-vis light irradiation. Among spinel ferrites, ZnFe2O4 presents the highest activity, readily operating without additional sacrificial reagents in photocatalytic detoxification of aqueous Cr(VI), which together with transient gas analysis and fluorescence spectroscopy results suggest a competitive formation of oxygen and hydroxyl radicals at the catalyst surface. These findings provide an essential tool for the delineation of the electronic structure-catalytic property relationship in spinel ferrite nanostructures offering intriguing possibilities for designing new photo catalytic systems for efficient environmental pollution purification and energy conversion.