In this work, the dioxirane system has been applied to the epoxidation of cyclohexene. The catalytic activity of acetone, butan-2-one and pentan-2-one presented as homogeneous catalysts or supported on inorganic and polymer materials was investigated. It was found that the rate of cyclohexene oxide formation increased in proportion to increasing ketone concentrations using acetone and butan-2-one. Because of the advantages of supported catalysts, ketones were chemisorbed or grafted onto a range of different supports including different forms of silica and various polymers. The presence of carbonyl groups on the surface of the supports was confirmed and their catalytic activity was evaluated. The turnover frequency of the grafted ketones were compared with that of the homogeneous catalysts and design criteria for the further development of supported ketone catalysts were established.