The surface of three different grades of commercial high-purity a-Al 2 O 3 powders produced by hydrolysis of aluminum alkoxide, which differ each other in SSA are evaluated by temperature programmed desorption mass spectrometry (TPDMS) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. For the DRIFT evaluation the powders were heated in situ under vacuum from 25 to 700 8C. The TPDMS spectra of desorbed H 2 O were obtained by heating the samples under ultra high vacuum at a rate of 20 K min K1 up to 1200 8C.The presence of hydrogen bonded water molecules, amorphous Al(OH) 3 and AlOOH structures, as well as associated and isolated hydroxyl groups on the surface of all the a-Al 2 O 3 powders investigated is demonstrated. On the surface of one of the powders the presence of crystalline Al(OH) 3 structures, as evidenced by an additional sharp peak in the H 2 O TPDMS spectrum, is confirmed. q