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Polystyrene (PS) and poly(methyl methacrylate) (PMMA) blends filled with octadecylamine-functionalized graphene (GE-ODA) have been fabricated to obtain conductive composites with a lower electrical percolation threshold according to the concept of double percolation. The dependence of the electrical properties of the composites on the morphology is examined by changing the proportion of PS and PMMA. Our results reveal that the electrical conductivity of the composites can be optimal when PS and PMMA phases form a cocontinuous structure and GE-ODA nanosheets are selectively located and percolated in the PS phase. For the PS/PMMA blend (50w/50w), the composites exhibit an extremely low electrical percolation threshold (0.5 wt %) because of the formation of a perfect double percolated structure. Moreover, the rheological properties of the composites are also measured to gain a fundamental understanding of the relationship between microstructure and electrical properties.