We have designed and engineered an environmentally sustainable ternary polymer blend with the mechanical properties comparable to high impact resistant conventional polymers under the guidance of the lattice self-consistent field model. In this blend system, poly(methyl methacrylate) (PMMA) was used as the compatibilizer for the poly(lactic acid) (PLA)/poly(butylene adipate-co-butylene terephthalate) (PBAT) blend. We characterized the compatibility of those components and found PMMA was miscible with PLA and partially compatible with PBAT, which allowed it to self-assemble to a nanoscale interfacial layer on the PLA/PBAT interface. This PMMA layer can significantly decrease the interfacial energy and strongly entangle with either PLA or PBAT, resulting in the strengthening of the interface and dramatically enhancement of the impact resistance of the ternary blend. The optimal mechanical performance was achieved when the total PMMA concentration was less than 10 wt %. Higher PMMA content embrittled the blend since the additional PMMA did not contribute to the minimization of the interfacial energy but remained in the PLA phase, increasing the glass transition temperature of the matrix.