Derivatization has great potential for the high-value utilization of cellulose by enhancing its processability and functionality. However, due to the low reactivity of natural cellulose, it remains challenging to rapidly prepare cellulose derivatives with high degrees of substitution. The “cavitation effect” of ultrasound can reduce the particle size and crystalline index of cellulose, which provides a possible method for preparing cellulose derivatives. Herein, a feasible method was proposed for efficiently converting regenerated cellulose to cellulose oleate with the assistance of ultrasonic treatment. By adjusting the reaction conditions including ultrasonic intensity, feeding ratios of oleic acid, reaction time, and reaction solvent, a series of cellulose oleates with degrees of substitution ranging from 0.37 to 1.71 were synthesized. Additionally, the effects of different reaction conditions on the chemical structures, crystalline structures, and thermal behaviors were investigated thoroughly. Cellulose oleates with degrees of substitution exceeding 1.23 exhibited amorphous structures and thermoplasticity with glass transition temperatures at 159.8 to 172.6 °C. This study presented a sustainable and practicable method for effectively derivatizing cellulose.