Owing to its biological significance, preparation of stable surface-confined catechol (CA) is a long-standing interest in electrochemistry and surface chemistry. In this connection, various chemical approaches such as covalent immobilization (using amine- and carboxylate-functionalized CA, diazotization-based coupling, and Michael addition reaction), self-assembled monolayer on gold (thiol-functionalized CA is assembled on the gold surface), CA adsorption on the ad-layer of a defect-free single-crystal Pt surface, π-πbonding, CA pendant metal complexes, and CA-functionalized polymer-modified electrodes have been reported in the literature. In general, these conventional methods are involved with a series of time-consuming synthetic procedures. Indeed, the preparation of a surface-fouling-free surface-confined system is a challenging task. Herein, we introduce a new and facile approach based on electrochemical demethylation of 2-methoxyphenol as a precursor on the graphitic surface (MWCNT) at a bias potential, 0.5 V vs Ag/AgCl in neutral pH solution. Such an electrochemical performance resulted in the development of a stable and well-defined redox peak at Eo' = 0.15 (A2/C2) V vs Ag/AgCl within 10 min of preparation time in pH 7 phosphate buffer solution. Calculated surface excess (16.65 × 10-9 mol cm-2) is about 10-1000 times higher than the values reported with other preparation methods. The product (catechol) formed on the modified electrode was confirmed by collective electrochemical and physicochemical characterizations such as potential segment analysis, TEM, Raman, IR, UV-vis, GC-MS, and NMR spectroscopic techniques, and thin-layer chromatographic studies. The electrocatalytic efficiency of the surface-confined CA system was demonstrated by studying hydrazine oxidation and sensing reactions in a neutral pH solution. This new system is found to be tolerant to various interfering biochemicals such as uric acid, xanthine, hypoxanthine, glucose, nitrate, hydrogen peroxide, ascorbic acid, Cu2+, and Fe2+. Since the approach is simple, rapid, and reproducible, a variety of surface-confined CA systems can be prepared. © 2020 American Chemical Society.