Characteristics of the catalytic activity in the dehydration of butanols of copper-containing sodium-zirconium-phosphates (NZPs), in which Na+ ions substitute for Cu2+ ions are obtained. It was found that in the 100-370°C region, the action energy of the reaction falls upon the transition through temperature T*∼ 300°C, above which the electrophysical and crystallographic properties of phosphates change. The observed dependences are explained by the center (which consists of copper with various positions in the phosphate network at T < T*and T > T*) taking part in the formation of carbonyl compounds. This indicates the presence of a ligand effect, i.e., to structural sensitivity of the dehydration reaction in the case of Cu-NZP catalysts. © 2011 Pleiades Publishing, Ltd.