light. Since then, research in this area has been greatly accelerated, being driven by searching of clean energy sources such as H 2 or other fuels, [1] solving the environmental issues with persistent organic pollutants in wastewater, [2] as well as in the applications for artificial photosynthesis such as CO 2 reduction, [3,4] N 2 fixation, [5] or photocatalytic therapy. [6,7] These intrinsic wide bandgap semiconductors usually show photocatalytic activity by UV light illumination with photon energy close to their bandgaps. The UV excitation generates electron-hole pairs in the photocatalyst, and they have to migrate to their surface and create radicals there, which can be used for the above-mentioned photocatalytic applications. However, only ≈4% of UV contributes to the solar spectrum falling on the earth surface, and photocatalytic response at longer wavelengths in the visible range becomes the major bottleneck for the efficient harvesting of solar energy.To expand the range of photocatalytic response further in the visible region for wide bandgap semiconductors such as TiO 2 and ZnO (E g = 3.37 eV), numerous studies were performed, using different strategies including intentional doping of transition metals, nonmetals, surface decoration with noble metals, and heterojunction. [8][9][10] The main route is to intentionally introduce interband defect levels (IDLs) by extrinsic doping of transition metals and nonmetals, [5] so that the low energy photons can be harvested via the IDLs, and generate carriers for the photocatalytic applications. A milestone in the development of visible light driven photocatalysts was reached in N-doped TiO 2 system, [11] and Asahi et al. [12] demonstrated in 2001 that the N-doped TiO 2 shows photocatalytic response up to a wavelength of 500 nm. However, only few investigations [13,14] about the photocatalytic activities of nondoped (intrinsic) ZnO have been demonstrated, and these studies use the IDLs introduced by the native defects (point defects and their complexes, extended defects, and surface states) to harvest the sub-bandgap low energy photons in the visible range.The dilemma of the IDLs is that on the one hand they can improve the light absorption in the sub-bandgap visible range, generate carriers via the IDLs, and are therefore beneficial for the photo catalytic processes, on the other hand, they serve simultaneously as recombination centers, through which the photogenerated electrons and holes recombine with each A novel route to synthesize large area ZnO/Zn(OH) 2 origami thin films at air/liquid interface is reported. ZnO materials derived from this route show the largest blue-shifted band-to-band emission at 3.85 eV (3.37 eV in bulk ZnO) so far, resulting from the quantum confinement in the ultrathin ZnO/ Zn(OH) 2 nanosheets. Interband defect levels (IDLs) related broadband photoluminescence is observed from UV to red region by excitation wavelength dependent photoluminescence measurements. The ZnO origami structures show photocatalytic methylene blue degradation (M...