Poly (lactic acid) (PLA)/poly (butylene adipate-co-terephthalate) (PBAT)/poly (propylene carbonate) (PPC) multi-phase blends were prepared by melt processing technique under the presence of compatibilizer with various composition. The effect on the physical and the mechanical property with/without ESO was characterized with spectrophotometric analysis, mechanical properties, thermal properties, rheological properties and barrier properties, and the structure-properties relationship was assessed. The functional groups of PPC were found to effective to improve an interaction with carboxyl/hydroxyl group of PLA/PBAT binary blends to enhance the mechanical and physical properties on multi-phase blend system. The presence of PPC in PLA/PBAT blend affected the reduction of voids on the interface phase resulting in enhancing the oxygen barrier properties. With addition of ESO, the compatibility of ternary blend was found to be enhanced since the epoxy group of ESO reacted with the carboxyl/hydroxyl group of PLA, PBAT, and PPC, and under the condition with critical content of 4 phr of ESO, the elongation behavior dramatically increased as compared to that of blends without ESO while affecting reduction of oxygen barrier properties. The effect of ESO as a compatibilizer was clearly observed from the overall performances of ternary blends, and the potential feasibility of the PLA/PBAT/PPC ternary blends as packaging materials was confirmed at this study.