The addition of urea in pre-cooled alkali aqueous solution is known to improve the dope stability of cellulose solution. However, its thermodynamic mechanism at a molecular level is not fully understood yet. By using molecular dynamics simulation of an aqueous NaOH/urea/cellulose system using an empirical force field, we found that urea was concentrated in the first solvation shell of the cellulose chain stabilized mainly by dispersion interaction. When adding a glucan chain into the solution, the total solvent entropy reduction is smaller if urea is present. Each urea molecule expelled an average of 2.3 water molecules away from the cellulose surface, releasing water entropy that over-compensates the entropy loss of urea and thus maximizing the total entropy. Scaling the Lennard-Jones parameter and atomistic partial charge of urea revealed that direct urea/cellulose interaction was also driven by dispersion energy. The mixing of urea solution and cellulose solution in the presence or absence of NaOH are both exothermic even after correcting for the contribution from dilution.