[VO](2+)-Exchanged Nafion(R) beads are efficient catalysts for the aerobic C-C bond cleavage of 2-hydroxycyclohexanone and 2-methylcyclo-hexanone in methanol and acetonitrile, respectively. Performances of the heterogeneous systems are similar to their homogeneous counterparts. However, diffusion limitations with these two substrates, especially for the higher vanadyl contents have led to the design of different mixed redox and acid solid catalysts. Blank tests using non-exchanged Nafion(R) in methanol show that primary and secondary alpha-hydroxyketones are easily converted to various methoxy derivatives which are prone to autoxidation. More selective oxidation occurs when both protons and vanadyl salts are involved. Bead size and the nature of the solvent used for the ion exchange are important. The leaching of the different solids is less for alpha-alkyl ketones in acetonitrile. (C) 2003 Elsevier B.V. All rights reserved.