Layered double hydroxides (LDHs) are important materials in the field of catalyst supports, and their surface hydroxyl functionality makes them interesting candidates for supporting well-defined single-site catalysts. Here, we report that the surface hydroxyl concentration can be controlled by thermal treatment of these materials under vacuum, leading to hydroxyl numbers (alpha(OH)) similar to those of dehydroxylated silica, alumina, and magnesium hydroxide. Thermal treatment of [Mg0.74Al0.26(OH)(2)](SO4)(0.1)(CO3)(0.03)center dot 0.62(H2O)center dot 0.04(acetone) prepared by the aqueous miscible organic solvent treatment method (Mg2.84Al-SO4-A AMO-LDH) is shown to yield a mixed metal oxide above 300 degrees C by a combination of thermogravimetric analysis, powder X-ray diffraction (PXRD), BET surface area analysis, and FTIR spectroscopy. PXRD shows the disappearance of the characteristic LDH 00l peaks at 300 degrees C indicative of decomposition to the layered structure, coupled with a large increase in the BET surface area (95 vs 158 m(2) g(-1) from treatment at 275 and 300 degrees C, respectively). Titration of the surface hydroxyls with Mg(CH2Ph)(2)(THF)(2) indicates that the hydroxyl number is independent of surface area for a given treatment temperature. Treatment at 450 degrees C under vacuum produces a mixed metal oxide material with a surface hydroxyl concentration (alpha(OH)) of 2.14 OH nm(-2) similar to the hydroxyl number (a(OH)) of 1.80 OH nm(-2) for a sample of SiO2 dehydroxylated at 500 degrees C. These materials appear to be suitable candidates for use as single-site organometallic catalyst supports.