Polymer-supported methyltrioxorhenium (MTO) systems are efficient catalysts for the oxidative functionalisation of cyclohexane and cyclopentane, derivatives with H2O2 as oxygen donor. Using poly (4-vinyl)pyridine and poly(4-vinyl)pyridine-N-oxide as MTO supports, cycloalkanol, cycloalkanediol, cycloalkanone and omega-hydroxy methyl ketone derivatives were obtained in different yields depending on the experimental conditions. Interestingly, cycloalkane dimers were selectively recovered in acceptable to good yields when the oxidation was performed with polystyrene-microencapsulated MTO catalyst. The EPR investigation suggests that the homolytic cleavage of the CH3-Re bond with formation of CH3 center dot radicals occurs inside the polystyrene capsule, indicating a possible role of methyl radical in the cycloalkane dimerisation pathway. (c) 2006 Published by Elsevier Ltd.