Cellulose Oleate (CO) was synthesized by acylating cellulose in homogeneous system with p-toluenesulfonyl chloride (Tos-Cl) and oleic acid. The structure of CO was characterized by FT-IR, and degree of substitution (DS) of CO was determined by saponiﬁcation method. Substituent distribution analysis was carried out with curve-fitting method, and the results indicated that acyl reaction of cellulose with oleic acid preferred to react at primary hydroxyl groups. The CO converted into films by casting. The mechanical properties of CO films were investigated. With the increase of DS, the tensile strength decreases gradually, but the tensile strain increases apparently.