Not yet reviewed by Pith; the record is open.

The single diamond (SD) network, discovered in beetle and weevil skeletons, is the 'holy grail' of photonic materials with the widest complete bandgap known to date. However, the thermodynamic instability of SD has made its self-assembly long been a formidable challenge. By imitating the simultaneous co-folding process of nonequilibrium skeleton formation in natural organisms, we devised an unprecedented bottom-up approach to fabricate SD networks via the synergistic self-assembly of diblock copolymer and inorganic precursors and successfully obtained tetrahedral connected polycrystalline anatase SD frameworks. A photonic bandstructure calculation showed that the resulting SD structure has a wide and complete photonic bandgap. This work provides an ingenious design solution to the complex synthetic puzzle and offers new opportunities for biorelevant materials, next-generation optical devices, etc.