The Electro-Fenton process (EFP) is an electro-mediated advanced oxidation process capable of degrading organic pollutants that persist in industrial or domestic wastewater. However, the implementation of this process in large scale is still not competitive. The development of a material acting simultaneously as a cathode and a heterogeneous catalyst was proposed in this study in order to enable the reuse of the catalyst (iron) and its straightforward separation from solution. A novel iron-rich clay-like material (heterogeneous catalyst) was used to coat carbon felt fibers (cathode). The synthesis of such material followed a procedure adapted from the literature. The powder isolated from the reaction media was characterized by FTIR, XRD and XRF that indicated the condensation of a 2:1 clay-like structure. SEM images revealed that this novel iron-rich clay-like material coated carbon felt fibers as a thin and continuous film. The novel composite remained stable upon submersion in aqueous solution in consideration of the negligible concentration of iron ions determined by ICP-OES. However, CV experiments uncovered that structural Fe(III) was electro-inactive. This observation corroborated with the negligible performance of this novel composite in heterogeneous EFP (HEFP) towards the iodinated contrast agent, iohexol. The use of methyl viologen (MV+2) as an electron mediator was possibly able to reduce structural Fe(III) while unable to improve the performance of this iron-rich clay-like modified electrode in the HEFP. Therefore, the mechanism behind the electron-transfer to, from and across this clay-like structure are topics to be further considered in future studies.