Ordered mesoporous silica materials gain high interest because of their potential applications in catalysis, selective adsorption, separation, and controlled drug release. Due to their morphological characteristics, mainly the tunable, ordered nanometric pores, they can be utilized as supporting hosts for confined chemical reactions. Applications of these materials, however, are limited by structural design. Here, we present a new approach for the 3D printing of complex geometry silica objects with an ordered mesoporous structure by stereolithography. The process uses photocurable liquid compositions that contain a structure-directing agent, silica precursors, and elastomer-forming monomers that, after printing and calcination, form porous silica monoliths. The objects have extremely high surface area, 1900 m2/g, and very low density and are thermally and chemically stable. This work enables the formation of ordered porous objects having complex geometries that can be utilized in applications in both the industry and academia, overcoming the structural limitations associated with traditional processing methods.