Despite being weak attractive forces, closed‐shell metallophilic interactions play important roles in the Group 11 metal complexes on their diverse structural and physical features. A plethora of experimental and computational studies has thus been dedicated to such weak attractive d10–d10 interactions, particularly aurophilic and argentophilic interactions. Although d10–d10 CuI–CuI forces had been recognized for four decades, cuprophilic interactions are less explored and they are best evidenced by single‐crystal X‐ray crystallographic analysis on CuI complexes and aggregates thereof, by which precise information about the Cu⋅⋅⋅Cu contacts, shorter than the sum of two van der Waals radii (3.92 Å) between the copper centers concerned can be obtained. Based on recently compelling experimental and spectroscopic evidence for intra‐ and intermolecular cuprophilic interactions in copper chemistry, the present Minireview summarizes recent progress in the past three decades in the synthesis and structures of multinuclear homometallic copper complexes, whereby supported and unsupported d10–d10 CuI–CuI interactions are at work.

Chemical bonding is central to the study of chemistry, and is one of the key concepts in understanding material structures, properties, and reactions. In their Minireview on page 8936 ff., Y.‐C. Tsai et al. summarize hitherto existing findings of cuprophilic interactions within dimeric Cu complexes as well as copper chain complexes of up to six copper centers.. Different factors having an impact on these interactions, such as ligand scaffolds, the nature of the ligand donor atoms, or the coordination number are discussed in detail.