Developments in the understanding of how materials behave enable us to design material structures to display specified properties. We introduce multilayered materials as systems in which new properties, not found in their constituents in bulk form, can emerge. The importance of transmission electron microscopy to determine structure-property relationships in nanoscale multilayers through characterization of their atomic and electronic structure is emphasized. Two examples of technologically useful multilayer systems are considered in more detail: hard coatings made from nitride multilayer films and the new structures and magnetic properties that are found in some metal multilayer systems. Finally, we discuss the future developments that are required to fully exploit the novel properties found in multilayered materials.