Supported sulfonic acids can be employed as efficient catalysts in the dihydroxylation of 1-methylcyclohexene with aqueous hydrogen peroxide, without the use of additional solvents, under mild condition. The reaction was deeply studied in terms of catalyst, H2O2/1-methylcyclohexene molar ratio, and percentage of aqueous hydrogen peroxide to achieve the best reaction conditions. Experimental results, catalytic efficiency, and spectroscopy data allow to advance some hypothesis on the reaction mechanism, based on the interaction, likely via H-bond, of hydrogen peroxide with the sulfate groups resulting from the deprotonation of supported sulfonic acids. (C) 2012 Elsevier Inc. All rights reserved.