Since the discovery of the aluminophosphate family of molecular sieves, [1] many other elements have been incorporated into these structures to form microporous materials (for example, zincophosphates and zirconium phosphates) and the preparation of these types of solids continues to be the focus of a large body of work. Zirconium phosphates are especially interesting as they exhibit unique properties in the fields of photochemistry, [2] molecular and chiral recognition, [3] biotechnology, [4] and catalysis. [5] Zirconium phosphates with one-, two-, and three-dimensional connectivities are usually prepared using a solvothermal approach in water or organic solvents as the mother liquid. The nature of the interaction between the solvent and reacting species is undoubtedly critical, not only for control over the final crystal structure of the products, but also their crystal size and morphology, [6] both of which are important for synthetic chemists and materials scientists. Choosing the proper solvent is vital to the success or failure of the attempted syntheses.Ionothermal synthesis, a new method for the preparation of aluminophosphate molecular-sieve analogues [7][8][9][10][11][12][13][14] and other materials, [15][16][17][18] was developed in 2004 and has interesting features and potential advantages over the traditional method of molecular-sieve synthesis. For example, the cation of the ionic liquid can act both as the solvent and the structure-directing agent, and synthesis can take place at ambient pressure, eliminating safety concerns associated with high solvent pressures. As there are at least a million binary ionic liquids and potentially more than 10 18 ternary ionic liquids and eutectic mixtures, [7] compared to only about 600 molecular solvents used for solvent thermal synthesis, this preparative method offers many opportunities for the synthesis of new porous frameworks by selecting solvents with different organic groups. In contrast to the large and wideranging studies that have been undertaken on the hydrothermal synthesis of molecular sieves, ionothermal synthesis has only begun recently. Nevertheless, the work that has been done shows exciting possibilities for the preparation of hitherto unknown materials for improved preparation of previously synthesized materials and for mechanistic studies.To the best of our knowledge, no description of the synthesis of zirconium phosphate compounds by the ionothermal method exists in the literature. In an attempt to synthesize this kind of solid material, a series of syntheses in deep eutectic solvents (DES) have been carried out using HF, zirconium(IV) oxychloride, and H 3 PO 4 as initial reactants. The addition of fluoride in the form of HF is relatively wellknown in the synthesis of open framework materials, and helps to solubilize all the starting materials in the reaction solvent. [7,19] As a result, three different frameworks have been successfully synthesized in the present study. Two of these compounds are new phases with chain and layer framework str...