This paper systematically investigates the influence of azeotropic solvent and reflux ratio on separation efficiency of DMC-CH3OH mixture after azeotropic distillation with various solvents: n-C7H16, n-C6H14, C6H12 (hexamethylene), CH2ClCH2Cl, CCl4 and C6H6, respectively. It is experimentally proved that azeotropic distillation method is highly efficient for the separation of DMC-CH3OH mixture. The results indicate that the composition of residue can be effectively regulated by modifying azeotropic solvent and reflux ratio. For azeotropic solvents investigated, the optimal reflux ratios are 7:1 or 8:1, which can lead to higher separation efficiency for DMC-CH3OH mixture. Moreover, at the same reflux ratio (7:1), the content and yield of DMC after azeotropic distillation are dependent on different solvents as the following order: CH2ClCH2Cl > CCl4 > C6H12 > C6H6 > n-C6H14 > n-C7H16.