The development of an alternate environmental friendly electrocatalyst suitable to replace the function of the ferrocene, ferricyanide and prussian blue-based redox-mediators is a challenging research interest. Herein, we introduced a novel method for synthesis of a highly redox-active surface-confined Hydroquinone on MWCNT modified glassy carbon electrode surface, GCE/MWCNT@H2Q using the earth-abundant lignocellulose-biomass product, syringaldehyde (Syn) by one-step potential cycling and potentiostatic polarization method in pH 7 phosphate buffer solution that can show an efficient ascorbic acid electrocatalytic signal better than the conventional redox-mediators suitable to use as an anode in biofuel cell and selective electrochemical sensor applications in neutral pH solution. This new electrode showed a well-defined redox peak at Eo′ = −0.15 V(A2/C2) and 0.0 V(A3/C3) vs Ag/AgCl corresponding to the redox-active molecular species of H2Q and its polymerized product, Poly-H2Q. Based on various physicochemical techniques like Raman, IR, TGA, DTA, TEM, GC–MS, H1-NMR and scanning electrochemical microscope imaging using substrate generation/tip-collection mode, it has been revealed that Syn-precursor underwent a demethoxylation and hydration upon the electrochemical preparation condition. It has been proposed that the Poly-H2Q is an active site for the selective electrocatalytic oxidation of AA in a neutral pH solution. © 2021 Elsevier B.V.