Transparent silica glass is one of the most essential materials used in society and industry, owing to its exceptional optical, thermal, and chemical properties. However, glass is extremely difficult to shape, especially into complex and miniaturized structures. Recent advances in three-dimensional (3D) printing have allowed for the creation of glass structures, but these methods involve time-consuming and high-temperature processes. Here, we report a photochemistry-based strategy for making glass structures of micrometer size under mild conditions. Our technique uses a photocurable polydimethylsiloxane resin that is 3D printed into complex structures and converted to silica glass via deep ultraviolet (DUV) irradiation in an ozone environment. The unique DUV-ozone conversion process for silica microstructures is low temperature (~220°C) and fast (<5 hours). The printed silica glass is highly transparent with smooth surface, comparable to commercial fused silica glass. This work enables the creation of arbitrary structures in silica glass through photochemistry and opens opportunities in unexplored territories for glass processing techniques.