Electropositive metals such as the alkaline earths or lanthanides are generally assumed to act largely as spectator cations in solid state compounds. In polar intermetallic phases, atoms of such elements are indeed often placed at the peripheries of anions or polyanionic fragments. However, they also show a pronounced tendency to cluster with each other in these peripheral regions in a manner suggestive of multicenter bonding. In this Article, we theoretically investigate the bonding schemes that underlie these cationic cluster arrangements, focusing on CaCu (whose two polymorphs are based on the intergrowth of the FeB- and CrB-types) and Ca2Cu (a Ca-intercalated derivative of CaCu). The structures of these phases are based on Cu zigzag chains embedded in matrices of Ca atoms arranged into increasingly well-developed fragments of closest-packed arrangements. Using reversed approximation Molecular Orbital (raMO) analysis, the Cu chains of both structures are revealed to be connected via nearly fully occupied Cu-Cu isolobal σ-bonds, such that the Cu atoms control 11.67 of the 13 and 15 electrons/formula unit of CaCu and Ca2Cu, respectively. Most of the remaining electrons are drawn to multicenter bonding functions in the Ca sublattices despite the availability of additional Cu 4p orbitals, indicating that the electronegativity difference between Ca and Cu is insufficient to achieve formal Cu oxidation states far beyond -1. The metallic nature of the Ca-based bonding subsystem is reflected in the raMO analysis by a plurality of resonance structures that can be generated from the occupied crystal orbitals. Across these bonding schemes, a separation of the electronic structure into largely self-contained Ca-Ca and Ca-Cu states is a consistent theme. This modularity in the bonding can be correlated to the ease with which this and related systems rearrange FeB- and CrB-type features, which may provide clues to identifying other intermetallic families with similar degrees of structural versatility.