Electrochemical hydrogenation is a challenging technoeconomic process for sustainable liquid fuel production from biomass-derived compounds. In general, half-cell hydrogenation is paired with water oxidation to generate the low economic value of O2 at the anode. Herein, a new strategy for the rational design of Ru/reduced graphene oxide (Ru/RGO) nanocomposites through a cost-effective and straightforward microwave irradiation technique is reported for the first time. The Ru nanoparticles with an average size of 3.5 nm are well anchored into the RGO frameworks with attractive nanostructures to enhance the furfural’s paired electrohydrogenation (ECH) and electrooxidation (ECO) process to achieve high-grade biofuel. Furfural is used as a reactant with the paired electrolyzer to produce furfuryl alcohol and 2-methylfuran at the cathode side. Simultaneously, 2-furic acid and 5-hydroxyfuroic acid along with plenty of H+ and e– are generated at the anode side. Most impressively, the paired electrolyzer induces an extraordinary ECH and ECO of furfural, with the desired production of 2-methylfuran (yield = 91% and faradic efficiency (FE) of 95%) at XFF = 97%, outperforming the ECH half-cell reaction. The mechanisms of the half-cell reaction and paired cell reaction are discussed. Exquisite control of the reaction parameters, optimized strategies, and the yield of individual products are demonstrated. These results show that the Ru/RuO nanocomposite is a potential candidate for biofuel production in industrial sectors.