The synthesis and catalytic activity of the polyfluorinated manganese, iron and cobalt porphyrins in homogeneous reaction and of these metallocomplexes supported on functionalized silica gel, polystyrene and montmorillonite K10 have been studied in oxidation of cyclooctane with molecular oxygen (as air) to cyclooctanone and cyclooctanol without the use of sacrificial co-reductant. The supported cobalt porphyrin is more active than the supported iron and manganese porphyrins and the activity of supported cobalt porphyrin is similar for all the supports. We have found that the silica as the support has reversed the order of activity of the supported catalysts in comparison to the metalloporphyrins in homogeneous system. The kind of support determines the product yields and the selectivity to cyclooctanone and cyclooctanol. We have also shown that the supported catalysts can be recycled and re-used. (C) 2004 Elsevier B.V. All rights reserved.