Rational material design requires a deep understanding about the relationship between the structure and properties of materials, which are both intimately related to their chemical bonding. Through the experimentally observable electron density, chemical bonding can be understood from experimental and theoretical points of view on an equal footing, and advances in accurate X‐ray diffraction measurements and computational techniques over the past decades have provided access to electron density distributions in increasingly complex functional materials. In this Review, selected electron density studies from the literature on a wide range of materials classes are presented, including studies of thermoelectric materials, high pressure electrides, coordination polymers and non‐linear optical materials. These studies demonstrate how detailed analysis of chemical bonding based on the electron density provides important understanding of materials beyond arguments based on structure and simple chemical concepts. In cases such as understanding the conducting properties of Zintl semiconductors or the effect of mutual electrical polarization in host–guest systems, it is clearly imperative to go beyond structure and examine the chemical bonding in detail. In the Review, the complementarity between theory and experiment is underlined, which allows for mutual validation of new chemical bonding concepts, and indeed experiment and theory may challenge each other based on the different strengths and weaknesses of each method.