In this work we have made use of the study of the interaction between Fe(TDCPP) + and the axial ligands OH - and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 10 - 6 mol Fe(TDCPP) + /g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin Fe I I I P species. In Fe(TDCPP)IPG 1 (containing 1.1 10 - 6 mol Fe(TDCPP) + and 2.2 10 - 4 mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP) + is present as a mixture of low-spin Fe I I I P and Fe I I P species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the Fe I I I P to the support partially blocks the reaction between Fe(TDCPP) + and PhIO, thus leading to the formation of only a small amount of the active species Fe I V (O)P + , while the Fe I I P species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP) + and decreasing the amount of imidazole in the support led to the obtention of high-spin Fe I I I P EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 10 - 6 mol Fe(TDCPP) + and 2.2 10 - 5 mol imidazole/g of IPG), together with low-spin Fe I I I P species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.