Micelle-templated mesoporous silica materials are rapidly becoming important in many fields of chemistry for hosting reactants or catalysts in confined space. Fine control of the pore size, wall structure, surface functionalization, defects, and morphology is needed for fine-tuning the pores as nanoreactors. We review the physical chemistry of solution silicate species and surfactants in the synthesis of mesoporous silicas. Controls in surfactant packing and liquid crystalline phase transformation can lead to various tailored synthesis strategies. Postsynthesis treatments further make more stable mesoporous materials.