The quest for solid-state materials with tailored chemical and physical features stimulates the search for general prescriptions to recognize and forecast their electronic structures providing valuable information about the experimentally determined bulk properties at the atomic scale. Although the concepts first introduced by Zintl and Hume–Rothery help to understand and forecast the bonding motifs in several intermetallic compounds, there is an emerging group of compounds dubbed as polar intermetallic phases whose electronic structures cannot be categorized by the aforementioned conceptions. These polar intermetallic compounds can be divided into two categories based on the building units in their crystal structures and the expected charge distributions between their components. On the one hand, there are polar intermetallic compounds composed of polycationic clusters surrounded by anionic ligands, while, on the other hand, the crystal structures of other polar intermetallic compounds comprise polyanionic units combined with monoatomic cations. In this review, we present the quantum chemical techniques to gain access to the electronic structures of polar intermetallic compounds, evaluate certain trends from a survey of the electronic structures of diverse polar intermetallic compounds, and show options based on quantum chemical approaches to predict the properties of such materials.