The intellectual and practical challenges of preparing enantioselective solids are discussed and two routes to the possible assembly of chiral inorganic structures highlighted. These synthesis methods are the imprinting of amorphous structures and the crystallization of chiral, crystalline, and microporous materials. For both types of solids, there is the potential to create chirality within the structure that may allow for long-term, robust use in catalytic reactions without significant loss of enantioselectivity.