Abstract: The physicochemical and catalytic properties of Cs1 – 2xNixZr2(PO4)3 (x = 0, 0.15, 0.25, 0.50) systems are studied. Double and triple nickel-containing phosphates with the NASICON structure are obtained by the sol–gel method. It is shown that these phosphates are active and stable isobutanol dehydration catalysts. The relationship between the catalytic activity in the dehydration reaction over triple cesium-zirconium phosphates and their crystallographic characteristics and surface acidity is established. It is shown that upon partial or complete replacement of cesium ions with nickel ions an increase in dehydration activity correlates with an increase in the number of acid sites determined by the pyridine adsorption titration method. © 2020, Pleiades Publishing, Ltd.