Inspired by opening soft drink cans, a one-pot method to prepare ZnO hollow spheres with double-yolk egg (DEH) architectures is developed. The bubble-assisted Ostwald ripening is proposed for the formation of these novel structures. Uniqueness of DEHs morphology led to greatly enhanced photocatalytic activity and photodetector performance. The newly developed synthetic concept and the obtained novel morphologies should pave the way towards the design and fabrication of other similar materials with enhanced properties for microelectronics, optoelectronics, and other applications.