The allyl chloride (ALC) epoxidation method for preparing epichlorohydrin (ECH) has outstanding advantages such as atom efficiency and environmental friendliness. However, the separation of ECH from the ECH/H2O/ALC/methanol (MET) quaternary system is still a great challenge for industrial interest. A hybrid extraction-distillation process is explored in this work to overcome the defects of high energy consumption and low efficiency in the process with separate extraction or distillation. At first, ALC is recommended as the solvent. Then the flow sheet of a hybrid extraction-distillation process was designed and subsequently optimized using Aspen Plus according to the total annual cost (TAC) minimum principle. Last, several different settings of the distillation column were explored and an optimal combination with an ECH purity of 0.998 and a maximum savings of 37.26% TAC was found. The results show that the hybrid extraction-distillation process is feasible and beneficial to industrialization of the proposed ALC epoxidation method.