The syntheses of C3‒substituted quinoxalin-2(1H)-one derivatives have been extensively studied for many years, whereas the strategies for the distant functionalization on the embedded fragrant ring have hardly ever been achieved. Herein, it’s reported that such a regioselective direct C7‒H functionalization might be enabled by electrochemical cascade sequences. Thus, quinoxalin-2(1H)-ones might be transformed into 7-thiocyanatoquinoxalin-2(1H)-ones in a CH3CN/H2O solvent combination through the use of an undivided cell at a relentless present with cheap graphite electrodes and commercially low-cost ammonium thiocyanate because the thiocyanate supply. This cascade sequences are constituted by the sequential cathodic discount on the C=N double bond using NH4SCN and H2O because the hydrogen donors, regioselective oxidative C7‒thiocyanation, and anodic oxidation of the C‒N single bond. The proposed mechanism has been supported by detailed cyclic voltammetry research and management experiments. This oxidant‒free technique not solely provides advantages by way of sustainability and effectivity in the direction of glorious useful group compatibility but additionally allows synthesis of C3-deuterated derivatives.