The upgrading of bio-oil model compounds such as guaiacol and phenol has obtained immense interest from the researchers in the field of thermochemical process as well as electrochemical process. The electrochemical method has some advantages for its mild condition, less coke formation, green process, and importantly in situ hydrogen production over thermochemical method. The researchers have endeavored to increase the C/H and C/O ratio in guaiacol or phenol hydrogenation process where deoxygenation was not achieved without coke formation. In this study, deoxygenation without any carbon loss has been demonstrated via electrochemical approach with additives. The addition of isopropanol enhanced the cyclohexane selectivity confirming hydrodeoxygenation at mild condition. Isopropanol acts as a co-reactant for hydrogen donation in hydrodeoxygenation of guaiacol, representing compound of fast pyrolysis oil and lignin derived oil in biomass conversion. Moreover, isopropanol not only affects reaction kinetics but also the vapor-liquid equilibrium of the solution. The presence of isopropanol shifts the boiling point of water-isopropanol-cyclohexane which transforms the stirred slurry electrocatalytic system into a stirred slurry electrocatalytic reactive-distillation (SSERD) system. These findings will benefit the process development for the upgrading of fast pyrolysis oil as well as lignin derived oil.