Compatibilization of blends by nanoparticles can impart the superior properties of the nanoparticles on the matrix and increase the compatibility of the blends. Manipulation of nanoparticles located at the interface is a premise and challenge to achieve. Poly(ethylene glycol) (PEG) was added to polylactide/poly(propylidene carbonate)/graphene oxide (PLA/PPC/GO) composites to manipulate the distribution of GO. By thermodynamic analysis and phase structure investigations, it was demonstrated that PEG could induce the transfer of GO from the PPC phase to the interface or PLA phase. Rheological investigations suggested that the entanglement density between the macromolecular chain and GO was improved, which enhanced the interactions of the macromolecular matrix and nanoparticles. Consequently, the compatibility and mechanical properties were improved significantly. In particular for the samples of PLA/PPC/GO 70/30/0.5 with 2 wt% PEG, the elongation at break was improved by a factor of 10 and the tensile strength was maintained at approximately 45 MPa. This simple physical method is expected to popularize the compatible role of GO in various industrial fields.