Epoxy is a widely used thermosetting resin that exhibits good mechanical strength, chemical resistance, and dimensional stability. In order to manufacture this resin, isopropyl alcohol (IPA) and excess epichlorohydrin (ECH) are used as a solvent and an indispensable raw material, respectively. However, ECH and IPA form a ternary azeotropic mixture in the presence of water, rendering it difficult to separate the materials with high purity via distillation. Therefore, a hybrid of pervaporation (PV)-coupled distillation was attempted to improve the epoxy manufacturing process. Silica-zirconia composite membranes were prepared by coating the α-Al2O3/SiO2-ZrO2 intermediate layer and the SiO2 separation layer, i.e., dip-coating was performed on the α-Al2O3 support and subsequently applied to the hybrid process. When the pervaporation process of distillate get from the epoxy by-product was applied, H2O selectivity for IPA/ECH was 15–30 and for H2O/aqueous impurities was 8–54, indicating that H2O for H2O/aqueous impurities permeated relatively faster than IPA/ECH. Therefore, pervaporation coupled distillation using an inorganic composite membrane was feasible for the selective removal of H2O/aqueous impurities in epoxy by-product mixture obtained from epoxy manufacturing.