Cellulose Stearate (CS) was synthesized by acylating microcrystalline cellulose (MCC) in homogeneous system with p-toluenesulfonyl chloride (Tos-Cl) and stearic acid (SA). The reactive conditions were discussed. The molar ratio of AGU:SA:Tos-Cl was the key factor which affected the degree of substitution (DS) of CS. In the present paper, CSs with DS ranging from 0.64 to 2.35 were prepared under mild condition. The structure of CS was characterized by FT-IR and 1H-NMR, and DS of CS was determined by traditional saponiﬁcation method and 1H-NMR, respectively. The solubility of CS was also investigated; the results showed that the higher DS of CS was, the easier CS dissolved in organic solvents. The thermal analysis was measured with DSC, and the results indicated that the glass transition temperature (Tg) and the maximum temperature of thermal decomposition (Tmax) of CS were dependent on DS.