Molecular distillation was used to recover ionic liquid (IL) 1-ally1-3-methylimidazolium chloride (AmimC1) in homogeneous cellulose acetylation. The five factors that affect the separation efficiency of molecular distillation, namely, feed flow rate, distillation temperature, feed temperature, wiper rotating speed, and distillation pressure, are discussed. The optimal recovery condition was determined via orthogonal experiments using an OA(9)(3(4)) design. The IL was recycled and reused 5 times in the homogeneous cellulose acetylation system under optimal conditions. The purity of recycled IL the 5th time reached 99.56%. FT-IR (Fourier transform infrared spectroscopy) and H-1 NMR (nuclear magnetic resonance) spectroscopy showed that the structure of the recovered IL is not changed. This work proves that AmimC1 has excellent reusability, and that molecular distillation is an effective method for recovering IL in homogeneous cellulose acetylation.