Fe(III) substituted Keggin type polyoxometalate in amorphous silica matrix, (n-C4H9)(4)N)(4)[PW11FeO39]/SiO2 (PWFe/SiO2), has been synthesized by sol gel method. The synthesized PWFe/SiO2 composite was characterized by various analytical and spectroscopic techniques. Results indicated that the primary Keggin structure remain after incorporation in silica matrix. As a heterogeneous catalyst, PWFe/SiO2 composite showed an elevated catalytic activity and selectivity with high to excellent yields for oxidation of alcohols into aldehydes by H2O2. The stability and reusability of the catalyst was very high, so these composites are suitable for the heterogeneous catalysis by hydrogen peroxide. (C) 2014 Elsevier B.V. All rights reserved.