The homogeneous liquid phase oxidation of indane and tetralin with hydrogen peroxide catalysed by tetrabutylammonium salts of iron(III)-substituted polyoxotungstates of general formula [XW11Fe(H2O)O-39](n-), X=P, Si or B is described. The system presented here gives rise to benzylic monooxygenation and dioxygenation products. Indane oxidation reactions produce also dehydrogenation and hydroperoxidation products. As a result, 1H-indene and indane hydroperoxide are formed. Interestingly, tetralin gives rise to the cleavage of carbon-carbon bond, producing 4-(2-hydroxyphenyl)butanal. In the present conditions, this aldehyde is probably arising from tetralin hydroperoxide. Depending on the reaction conditions, moderate selectivities for the corresponding ketones are obtained, affording conversions as high as 59% and 34% for indane and tetralin, respectively. In order to understand the reactions pathway, the oxidation of 1-indanol, 1-indanone, 1H-indene, 1-tetralol and 1-tetralone is also carried out with an iron(Ill)-substituted polyoxotungstate as catalyst and H2O2 as oxidant. The results show that 1-indanol and 1-tetralol give an important contribution for the formation of the corresponding ketones. As far as we know, the use of iron-substituted polyoxotungstates in the oxidation of these arenes is presented for the first time. (C) 2009 Elsevier B.V. All rights reserved.