AbstractPoly(butylene adipate‐co‐terephthalate) (PBAT) nanocomposites with poly(propylene carbonate) (PPC) and graphene oxide (GO) are fabricated by melt blending. A dual‐continuous network structure is obtained via adding reactive compatibilizer and nanofillers, which not only dramatically reduce the conductivity percolation threshold of nanocomposites but also improve its mechanical properties. The compatibility of PBAT and PPC is improved owing to the partial thermally reduced GO (PrGO) with the residual oxygen‐containing functional groups on its surface. The epoxy groups of the reactive compatibilizer (Jc‐ADR) react with the terminal groups of polymers to increase the interfacial adhesion. The characterization analysis by morphology, rheology, mechanics, DMA, and conductivity indicates that the formation of the dual‐continuous network is attributed to the synergistic effect of PrGO and Jc‐ADR. Furthermore, a remarkable enhancement in barrier properties is obtained with the addition of PrGO. Compared with PBAT/PPC blends, the water vapor permeability (WVP) decreases by nearly 1 order of magnitude after adding 1.0 wt% PrGO. This will offer a possibility for the development application of PBAT and PPC in a barrier and antistatic packaging field.