The structure of the photoluminescent compound hexaaquadichloridoneodymium(III) chloride has been redetermined from single‐crystal X‐ray diffraction data at 100 K, with the aim of providing an accurate structural model for the bulk crystalline material. The crystal structure may be described as a network of [NdCl2(H2O)6]+ cations with distorted square‐antiprism geometry around the NdIII centre. The NdIII cation and the nonbonded Cl− anion are both located on twofold symmetry axes. The crystal packing consists of three different neodymium pairs linked by a three‐dimensional network of O—H...Cl intermolecular interactions. The pair distribution function (PDF) calculated from the experimentally determined structure is used for the discussion of the local structure.