The present work reports a simple and rapid disassembly/reassembly approach at room temperature to tailor functional metal oxides of 2D and 3D architectures. Precise control over the morphology of nanomaterials is critical yet challenging. The present work reports an efficient approach to tailor the architecture of nanostructures. The process involves rapid disassembly/reassembly of an unstable metal-based coordination polymer (MCP) by controlling the kinetics of the reassembly process. The synthesis procedure delivers unprecedented polycrystalline nanostructures, e.g. , holey 2D CeO 2−x nanosheets, with precisely tailored thicknesses in the range of 10–100 nm, and hollow 3D pseudo-octahedra and spheres. The consequent high surface areas and pore volumes, short diffusion distances, and high defect densities of the holey 2D CeO 2−x indicate significant densities of active sites. This holey architecture exhibits rapid CO conversion and outstanding solar light photocatalytic performance. This approach of directed assembly offers a template-free, controllable, and cost-effective approach to achieve engineered CeO 2−x architectures, which are nearly impossible through existing approaches.