The location of the divalent nickel cation exchanged in low amount in dehydrated NaX is identified by a combination of experimental (XAS) and theoretical (DFT) approaches. The Ni-O and Ni-T distances as well as the coordination numbers evaluated from experiments are in good agreement with the predicted models obtained from calculations. After dehydration, the migration of Ni2+ towards the hexagonal prism is confirmed and three distinct possible nickel sites are predicted. The results show the tendency of Ni2+ to get closer to the most basic framework oxygen atoms. (C) 2011 Elsevier B. V. All rights reserved.