Zinc perchlorate, diorganodiphosphates (POP2−), and chelating ligands L (L = 1,10‐phenanthroline, neocuproine, 2,2′‐bipyridine, oxinate) yield three types of ternary complexes. Type 1 (L2Zn·POP) contains octahedral zinc bound by the diphosphate as an OPOPO chelate ligand. Type 2 (LZn·POP) consists of dimeric complexes containing five‐coordinate zinc, with the diphosphates acting as OPOPO chelate ligands for one zinc ion and as OPO bridges between two zinc ions. Type 3 (L2Zn2·POP), observed only for oxinate, is proposed to contain two five‐coordinate zinc ions bridged by the diphosphate as a tetradentate ligand.