1,10-Phenanthroline (Phen) is a well-known benchmark ligand and has often been used in the coordination chemistry for the complexation of transition metal ions, such as Fe2+, Ni2+, and Co2+. Because the electro-oxidation potential of Phen is much higher (>2 V versus Ag/AgCl) than the water decomposition potential, i.e., ∼1.5 V versus Ag/AgCl, in pH 7, it is practically difficult to electro-oxidize Phen in aqueous medium using any conventional electrodes, such as glassy carbon electrode (GCE), gold, and platinum. Interestingly, herein, we report an unexpected oxidation of Phen to a highly redox active 1,10-phenanthroline-5,6-dione (Phen-dione) and its confinement on a multiwalled carbon nanotube (MWCNT)-modified glassy carbon electrode (GCE/MWCNT@Phen-dione) surface by potential cycling of Phen-adsorbed GCE/MWCNT (GCE/MWCNT@Phen) from -1 to 1 V versus Ag/AgCl in pH 7 phosphate buffer solution. GCE/MWCNT@Phen-dione showed selective recognition of copper ion (GCE/MWCNT@Phen-dione-Cu2+) by catalyzing the hydrogen peroxide reduction reaction in a neutral pH solution. The precise structure of the Phen electro-oxidized product has been identified after characterizing the electrode and/or ethanolic extract of the product by various techniques, such as Raman, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) (for copper complex), liquid chromatography-mass spectrometry (LC-MS), electrospray ionization-mass spectrometry (ESI-MS) (for copper complex), cyclic voltammetry (CV), and in situ electrochemical quartz crystal microbalance (EQCM) and comparing electrochemical behavior of several control compounds, such as phenanthrene and 9,10-phenanthrenequinone. It is concluded that the product formed is 1,10-phenanthroline-5,6-dione, wherein the dione position is ortho to each other and the copper ion is complexed with nitrogen of the phenanthroline ring. With extended electrochemical oxidation of a structurally similar ligand, 2,2′-bipyridine failed to show any such electrochemical dynamics. Finally, applicability of GCE/MWCNT@Phen-dione-Cu2+ for electrochemical sensing of hydrogen peroxide in a couple of real samples is successfully demonstrated. © 2014 American Chemical Society.