Method of synthesis of photonic band gap (PBG) materials. The synthesis and characterization of high quality, very large scale, face centered cubic photonic band gap (PBG) materials consisting of pure silicon, exhibiting a complete three dimensional PBG centered on a wavelength of 1.5 .mu.m. This is obtained by chemical vapor deposition and anchoring of disilane into a self-assembling silica opal template, wetting of a thick silicon layer on the interior surfaces of the template, and subsequent removal of the template. This achievement realizes a long standing goal in photonic materials and opens a new door for complete control of radiative emission from atoms and molecules, light localization and the integration of micron scale photonic devices into a three-dimensional all-optical micro-chip.