Excitation and emission spectra of Mn2+ ions in calcium chloride have been studied using the photoluminescence technique. From a crystal-field analysis of the excitation spectrum is inferred that the Mn2+ ion occupies the Ca2+ cation site forming octahedral MnCl64- complexes. A ligand inward relaxation around the Mn2+ is noticed as a consequence of smaller ionic radius of Mn2+ than that of host cation. This investigation supports the usefulness of crystal-field spectra for obtaining information on the local structure of impurity ions in ionic lattices. © 2004 Elsevier B.V. All rights reserved.