Synthesis and physico-chemical characterization of a pure magnesium phosphate (MgP) prepared by coprecipitation, and MgP modified by introduction of cobalt–molybdenum (4–12wt.% of MoO3 with the Co/Mo ratio fixed at 0.5) have been carried out. The structural properties of these catalysts were characterized by X-ray diffraction, their textural properties were determined by N2 adsorption–desorption isotherms and the dispersion of cobalt–molybdenum was studied by XPS spectroscopy. Their acid properties have been investigated by in situ FT-IR spectroscopy of adsorbed molecules, often, 2,6-dimethylpyridine (pKa=6.7), pyridine (pKa=5.3). Co–Mo incorporation leads to a modification in the MgP acid–base properties, especially on the acid sites type and number. Thus, lower loading of cobalt–molybdenum species decreased the number of strong Lewis acid sites whereas higher loading increased it. It was found that Lewis acid sites on magnesium phosphates play an important role in the isomerization of 3,3-dimethylbut-1-ene.The 3,3-dimethylbut-1-ene (33DMB1) conversion increases with the reaction temperature from 493 to 653K for MgP, but decreases after 573K for MgP supported by Co–Mo. A linear relationship between both types of acid sites and conversion values was found. The deactivation of the catalysts appears at high reaction temperature (>573K).