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Electrically conductive and flame-retardant maleic anhydride grafted high-density polyethylene (MA-HDPE) nanocomposites with satisfactory mechanical properties are fabricated by melt compounding MA-HDPE with polyethyleneimine (PEI)-modified reduced graphene oxide (PEI@RGO) as the conductive nanofiller and brominated polystyrene (BPS) as the flame retardant. The modification with PEI significantly improves the interfacial compatibility and dispersion of the RGO sheets in the MA-HDPE matrix, leading to electrically conductive nanocomposites with enhanced mechanical properties. Furthermore, the addition of 25 wt% of BPS makes the nanocomposite flame-retardant with a UL-94 V-0 rating. Thus, the multifunctional RGO/MA-HDPE nanocomposites with good electrical, flame-retardant, and mechanical properties would have potential applications in construction and pipeline fields.