In this study, a novel hybrid method of hydrothermal electrolysis implemented for the decomposition of microcrystalline cellulose (MCC) into high value added chemicals such as levulinic acid, 5-hydroxymethylfurfural (5-HMF), and furfural. The hypothesis of the study was that, when direct current (DC) is applied the formation of ionic and radical species can alter the hydrolysis of cellulose. Based on this hypothesis, the purpose of the study was to build an integrated method of hydrothermal electrolysis that can lower energy requirement of cellulose hydrolysis by altering the selectivity. In order to investigate the individual and coupled effect of operating parameters such as reaction temperature (170-200 ℃), time (30-120 min.), electrolyte concentration (1-50 mM H2SO4), constant current (0-2 A), statistical analysis was conducted by a fractional factorial design. Analysis of variance (ANOVA) test was applied to the main hydrolysis products yields of MCC, total organic carbon (TOC) and cellulose conversion. Based on the response surface plots, 1A of current at 200 ºC maximized TOC yield and cellulose conversions to 62% and 81%, respectively. In order to enhance the selectivity, constant voltage (2.5, 4.0 and 8.0 V) was applied at 200℃. Application of 2.5 V increased TOC (54%) and alter the selectivity of 5-HMF (30%) and levulinic acid (21%). The structural changes in solid residues were analyzed by Fourier Transform Infrared Spectroscopy (FTIR) and found that MCC particles functionalized by carboxylic acid and sulfonated groups by application of 2.5 V. Therefore, change in the selectivity values were conducted with the functionalization of MCC particles due to applied voltage under sub-critical conditions.