The reduction of biomass derived phenols by electrochemical catalysis is an ideal route toward sustainable biorefinery processes. Herein, we present a highly efficient and selective electrochemical catalytic hydrogenation (ECH) of guaiacol by using N-doped carbon supported PtRu catalyst (PtRu/NC). The electrocatalyst with massive defects by N-doping and plentiful edges was prepared by the combining of collagen hydrolysis, templating carbonization , and Pt/Ru-tannic acid surface modification, which exhibits electrochemical hydrogenation of guaiacol to cyclohexanol with an enhanced productivity (100 %), cyclohexanol selectivity (78.5 %) and Faradic efficiency (FE, 65.4 %) at −200 mA/cm 2 . Moreover, the superb stability and reusability of PtRu/NC ensure the potential long-term application, which maintains stable after 2000 cycles LSV test and retains the productivity (97.8 %) and FE (65.2 %) after 5 electrolytic cycles. In-situ diffuse reflection Fourier transform infrared spectrum (DRIFTS) reveals that the introduction of Ru in PtRu/NC promotes the aromatic ring activation, and the synergy between Pt and Ru enhanced the adsorption of H* and substrate, thereby enhance the ECH activity and accelerate the reaction. This work provides a novel strategy for the rational design of highly efficient catalyst for the refining of biomass derived phenols.