Commercial carbon felt (CF) substrates have been modified with iron-rich MFI zeolite nanoseeds prepared by a solvothermal microwave-assisted synthesis method. The as-prepared material (MFI@CF) was characterized by TGA, XRD, SEM, and used as both cathode and catalyst in heterogeneous electro-Fenton (EF) process for the abatement of a biorefractory model dye pollutant, Acid Orange 7 (AO7). The complete degradation of 200 mL AO7 (0.1 mM) was achieved after 40 min contact with the modified material instead of more than 120 min with the pristine one. The proposed catalytic system exhibited an attractive activity with the total organic carbon (TOC) removal reaching 26.6% after 8 h at pH 6.5. The present results prove a promising efficiency of iron-rich MFI@CF material for a “green” EF treatment of water pollutants, avoiding the use of any non-recyclable soluble Fe²⁺ salt classically required as EF catalyst.