To elucidate the role of urea in dissolution of cellulose in aqueous alkali-urea solvent, the dissolution process was monitored by differential scanning calorimetry and X-ray diffractometry. Urea had no direct interaction with cellulose in dissolution process, but promoted the decrease of crystallinity. Moreover, the addition of urea increased the dissolved fraction of cellulose in the solvent by 1. 5-2. 5 times and improved the thermal stability of the solution. Urea might help alkali hydrate to penetrate into crystalline region of cellulose by stabilizing the alkali-swollen cellulose molecules, leading to an increase in dissolved fraction of cellulose. This stabilization may be due to the local accumulation of urea on the hydrophobic surface, preventing the hydrophobic association of dissolved cellulose molecules. © 2012 Springer Science+Business Media Dordrecht.