Multiwalled carbon nanotubes containing an iron impurity (2.1 wt %) (MWCNT‐Fe*) were used to modify a glassy carbon electrode (GCE/MWCNT‐Fe*), which was subsequently exploited for the electrochemical oxidation of benzene (BZ) to redox‐active and surface‐confined quinones (BZO) in H2O2 containing pH 2 HCl–KCl. Physicochemical and electrochemical characterization methods, such as transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, UV/Vis spectroscopy, liquid chromatography coupled mass spectroscopy, and cyclic voltammetry studies with naked Fe3+/2+, catechol (CA), and hydroquinone (HQ), evidenced that, in the presence of H2O2, the intrinsic iron impurity in MWCNT‐Fe* follows the electro‐Fenton reaction to oxidize BZ to BZO (CA+HQ) on the surface of MWCNT‐Fe* (i.e. GCE/MWCNT‐Fe*@BZO). Electro‐catalytic oxidation of hydrazine was demonstrated as a model system for the application of the GCE/MWCNT‐Fe*@BZO catalyst.