The adsorption of tert-butyl hydroperoxide over zirconia, alumina, vanadia-zirconia and vanadia-alumina catalysts from gas phase has been investigated by FT-IR spectroscopy. The formation of surface tert-butylperoxide species has been observed. These species give rise to different kinds of transformation, producing surface tert-butoxide, formate, acetate and acetone species, to which correspond gas-phase acetone, methanol, isobutene, water and (probably) oxygen. Surface vanadyl species are involved in this chemistry and enhance the rate of these reactions. (C) 2009 Elsevier B.V. All rights reserved.