A new procedure for increasing surface area and basicity of MgO has been developed in this work, leading to a tailored catalyst for the self-condensation of acetone. The preparation method, consisting on the hydration/dehydration of periclase, was optimized varying the activation procedures. The effect of the precursor (magnesium oxide or magnesium carbonate) and the thermal treatment on the morphological properties and the basic sites distribution was characterized. In particular, CO2 calorimetry data attributed the increase of basic sites mainly to the increase in surface area. The material was tested for the base-catalyzed self-condensation of acetone, obtaining high conversions and selectivities towards the products of most industrial value, the isophorones. The selectivity reached to trimers at 723 K was almost 50%, and towards isophorones, of more than 30%. (C) 2013 Elsevier B.V. All rights reserved.