Technical polycrystalline sintered Al2O3 (90%) substrates have been irradiated, in a vacuum chamber, at grazing incident angles (similar to 30 degrees), with pulsed ArF (lambda = 193 nm, hv = 6.4 eV) excimer laser, at different fluences and numbers of pulses, to modify the structure and morphology of the surface. Vacuum, inert gas and oxygen atmospheres, at different substrate temperatures, similar to 25 degrees C and similar to 700 degrees C, have been used to study surface chemistry and morphology modifications induced by laser energy. Surface chemistry has been analysed by XPS spectroscopy. Morphological modifications have been studied by SEM/EDS microscopy. Changes in surface roughness have been quantified by a standard profilometer.