C5H14NO center dot ZnCl(HPO3) arose from an unexpected reaction in which a component of the ionic liquid mixed solvent was incorporated into a hybrid structure in which cholinium (C5H14NO+) cations interact with [ZnCl(HPO3)](-) macroanionic layers by way of O-H...O hydrogen bonds. The inorganic layers display a 4 . 8(2) topology. (c) 2007 Elsevier B.V. All rights reserved.