NaHSO4 center dot SiO2 was found to be an efficient catalyst for the synthesis of gem-dihydroperoxides from ketones and aqueous (50%) H2O2 under mild and heterogeneous conditions at room temperature within a short period of time. The method presented here has the advantages of environmental benignancy, good to excellent yields and simple operational procedure. (C) 2008 Elsevier B.V. All rights reserved.