The electro-Fenton oxidation process was used to treat organic pollutants in industrial waste-water as it is one of the most efficient advanced oxidation processes. The novel cell in this process consists of a prepared PbO2 electrode by electrodeposition on graphite substrate and carbon fiber modified with graphene as a cathode. X-ray diffraction, fluorescence, analysis system, atomic force microscopy, and scan electron microscopy were used to characterize the prepared anode and cathode. XRD patterns clearly show the characteristic reflection of the mixture of α - and β phases of PbO2 on graphite and carbon fiber, and AFM results for cath-ode and anode present that PbO2 on graphite substrate and graphene on carbon fiber surface are on a nanoscale. Contact angle measurement was determined for the carbon fiber cathode before and after modification. The anodic polarization curve showed a higher anodic current when utilizing the PbO2 anode than the graphite anode. Phenol in simulated wastewater was removed by electro-Fenton oxidation at 8 mA/cm2 current density, 0.4 mM of ferrous ion con-centration at 35 °C up to 6 h of electrolysis. Chemical oxygen demand for the treated solution was removed by 94.02% using the cell consisting of modified anode and cathode compared with 81.23% using modified anode and unmodified cathode and 79.87% when using unmod-ified anode and modified cathode.