An efficient green route for the synthesis of phenol from benzene has been reported over Fe3+/Mgo catalysts under mild conditions. Fe3+/MgO catalysts are prepared and well characterized using EDX, XRD, FTIR, surface area analysis pore volume determination and UV-vis diffuse reflectance studies. Activity of these systems towards single step oxidation of benzene to phenol at low temperature using H2O2 has been analyzed. The catalysts exhibited interesting oxidizing ability which has been attributed to Fe(III) dispersed in amorphous form as isolated units on MgO. Possibility of homogeneous nature of catalysis through leached Fe3+ ions has been ruled out by confirming the absence of Fe3+ in liquid phase, and the heterogeneous nature of catalysis has been confirmed. The decomposition of H2O2 by the catalysts has been studied. Reusability of the system is assured carrying out multiple runs using the recycled catalyst. The activity has been analysed towards reactants with various substituents in benzene ring. A metalloperoxide formation on the surface of MgO through heterolytic cleavage of H2O2 has also been suggested for the reaction. (C) 2009 Elsevier B.V. All rights reserved.