Truly hierarchical materials, as common in nature, can only be the designed by understanding and controlling the chemical and physical interactions between the constituting components over multiple length scales. To study the development of morphology and structure in such multi-component architectures by chemical synthesis, self-organization and directed assembly we make use of our expertise in advanced electron microscopy. In this talk our approaches to the quantitative multiscale imaging of these hierarchical materials are discussed. Particular emphasis is placed on smart data acquisition strategies to prevent sample damage by the electron beam, improve image contrast and overcome sampling limitations common to electron microscopy to derive quantitative structural descriptors that can be used to understand and tune assembly and resulting macroscopic functional properties.