AbstractCornstalk cellulose was liquefied in sub- and supercritical ethanol using an autoclave at 320 °C with 160 mL of ethanol. The effects of reaction time on esters formation during cellulose liquefaction were investigated. The yield of esters was 10.0% at 30 min, increasing to 19.1% after 60 min. Ethanol favored esters formation from cellulose liquefaction. The liquid products at different reaction time were analyzed by FT-IR and GC/MS. The results showed that many free radicals were produced in sub-/super-critical ethanol interactions. Cellulose was converted to active cellulose, which was transformed into large molecular acids by dehydration, decomposition, ring-opening reactions, isomerization, and aldol condensation, and then formed ethyl esters such as ethyl lactate by esterification. In addition, ethyl esters were decomposed to acids, alcohols, and other compounds with increasing reaction time in the presence of ethanol free radicals. Using these results, a reaction network for the formation of ethyl esters from cellulose in sub- and supercritical ethanol was proposed.