Since the development of the laddering principle in the mid‐1980s, it has become a useful concept for describing structural features in a wide variety of organoalkali metal (particularly organolithium) and other main‐group element oligomers. Here a brief account of the laddering principle is given, and a two‐stage approach to understanding structural diversity is described for several lithium heterocarboxylates. “Primary laddering” describes the initial aggregation of monomeric units, whereas “secondary laddering” deals with the assembly of these primary laddered units into larger structures. Both homo‐ and heteromolecular clusters can be formed by these processes. In this context, several examples are discussed, with particular emphasis on the effects of solvation and heteroatoms.