Techniques for producing a glass structure having interconnected macroscopic pores, employing steps of filling polymerizable glass precursors into pores in a polymeric structure having interconnected macroscopic pores; polymerizing the precursors; and decomposing the polymers to produce a glass oxide structure having interconnected macroscopic pores. Further techniques employ steps of exposing portions of a photosensitive medium including glass precursors to an optical interference pattern; polymerizing or photodeprotecting the exposed portions and removing unpolymerized or deprotected portions; and decomposing the polymerized or deprotected portions to produce a glass structure having interconnected macroscopic pores. Techniques for filling pores of such glass structure with a material having a high refractive index, and for then removing the glass structure. Structures can be produced having interconnected macroscopic pores and high refractive index contrasts, which can be used, for example, as photonic band gaps.