The field of intermetallic materials offers a wide range of structural diversity as well as a rich bounty of important properties like superconductivity and magnetism. Despite progress made in some systems, particularly thermoelectrics, the structure-property relationships remain largely elusive due to the extensive variety of atomic arrangements and properties that arise. In this dissertation, we aim to understand how form affects function in intermetallics through an approach familiar to inorganic molecular chemists: the analysis of directional bonding. Despite the impression that their bonding is completely delocalized, intermetallics in fact exhibit a mixture of covalent, ionic and metallic interactions. Bonding in intermetallics can then be considered in terms of its deviation from the Lewis dot-like depictions of fully localized models of the actual electronic structure. The electronic structure can be represented as a bonding scheme for an atom where valence electron pairs are localized between atom pairs (either homoatomic or heteroatomic), which represent the bonding orbitals, or on the atom itself, representing the nonbonding orbitals. As the assigned bonding scheme based on either type of interaction is equivalent in all symmetry related atoms, bonding in intermetallics can be discussed in terms of networks of these homoatomic or heteroatomic bonding schemes. Of course, intermetallics are not limited to a single bonding network as multiple networks may be necessary to depict the full electronic structure of a phase. Bonding analysis, then, in intermetallics can also involve an investigation into the interactions of the various bonding networks. The research within this dissertation aims to understand how the electronic structure, as represented by the bonding networks, affects the properties of intermetallic materials by studying systems that optimize their networks or allow for various interactions between their networks. Chapters 2 and 3 explore two possible types of interactions: competing and cooperating. In Chapter 2, the observed competition between the Co-Co and Si-Si bonding networks within a new polymorph of a previously reported GdCoSi2 phase causes an inherent weakness in the Co-Co bonds, which we exploit to trigger a reversible diffusionless phase transition. Chapter 3 focuses on the cooperative interactions between bonding networks. From calculations of the electronic structures of body centered cubic (bcc) Mo, and its binary isoelectronic variant, ZrRu, a picture emerges of two 18-electron resonance structures, the relative weights of which are determined by the electronegativity differences of the elements in the structure. The resonance formalism connects the work on the transition metal rich CsCl-type phases to the previous studies of bonding in isostructural transition metal poor compounds by presenting a continuum where the prevalence of the second resonance structure changes as a function of the availability of d orbitals to participate in bonding for one of the elements. In Chapter 4, the structural mechanisms by which a phase can optimize a single dominant bonding network are investigated. The nonstoichiometry of an Al column in a promising thermoelectric material, FeAl2.6, is linked to the valence electron count dictated by the Fe-Fe bonding network. The analysis is further supplemented by DFT-Chemical Pressure (CP) calculations, which shed light on the extensive positional disorder within the Al column and possible strategies to induce ordering. The final chapter departs from the general discussion of bonding, but continues along the topic of disorder, focusing on substitutional disorder. Using CP, a coloration pattern of a new Ru-substituted Y2Co17 ternary variant is explained as a strategy by the structure to optimize its bond distances. The insights gained open a possibility of guiding the synthesis of ternary variants of binary phases through the prediction of possible substitution patterns.