This work reports a promising and sustainable method for valorization of abundantly available biomass feedstocks to overcome the thermodynamic high energy barrier of the OER via glucose electrolysis as a proxy anodic reaction, thereby driving the energy-efficient water splitting for green hydrogen generation. For this, a robust and efficient MIL-88B(Fe) based electrocatalyst is engineered via Cu doping. The ultrasonically prepared Cu-doped@ MIL-88B ink when drop-cast on nickel foam (NF) produces thin nano-porous 2D-sheet like films having a thickness of ca. 300 nm and demonstrates an excellent glucose oxidation reaction (GOR) with a lower potential of 1.35 V versus RHE at 10 mA cm-2. In addition, this electrode shows outstanding long-term electrochemical durability for 50 h and exhibits the maximum GOR current load of 350 mA cm-2 at 1.48 V vs. RHE, while the pristine MIL-88B based electrode exhibits a current load of only 180 mA cm-2 at the same potential bias. The remarkably higher current density after doping indicates an accelerated GOR, which is ascribed to the electronic structure modulation of the Fe nodes by Cu, thereby enhancing the active sites and charge transport characteristics of the frameworks. Most importantly, the MOF-based electrodes demonstrate the occurrence of the GOR prior to the OER at a large potential difference, hence assisting the energy-efficient water splitting for green hydrogen production.