Imidodiphosphates ⊖N[PO(OR)2]2 and Imidodiphosphonates ⊖N[POR2]2 are effective chelating ligands for a variety of metal cations including even Na⊕, for which a lipophilically wrapped hexameric polyion cluster has been structurally characterized. The corresponding hexameric lithium and polyrubidium ion complexes reported here exhibit considerable structural differences: The rather small Li⊕ cations of coordination number five and tetraphenylimidodiphosphate form an isolated hexameric aggregate analogous to the Na⊕ one, whereas the larger Rb⊕ with coordination number seven and (3,4-dimethylphenyl)substituents crystallizes as a chain polymer. Based on the crystal structures, the dominant Coulomb attractions between cations and anions, the spatial requirement of the ligands and the essential phenyl/phenyl interactions in their lipophilic skin are discussed