Two types of layered zirconium polyimines have been synthesized. Monophosphonic acid head groups attached to polyimine chains form layered compounds with Zr-(IV) salts in which the Polyimine chains form bilayers in the interlamellar space. Upon protonation, the layers disperse, forming colloidal solutions. These free-floating polyimines readily encapsulate large polyvalent anions, accompanied by quantitative precipitation. Diphosphonic acids cross-link the layers and behave as insoluble anion exchangers in acid solution and as cryptates in neutral or alkaline media.