AbstractThe demand for polymers with antibacterial properties is increasing in food packaging industry and medical supplies. Antibacterial additives without toxic metal ion release are crucial for health and safety but still have challenges. Herein, polypropylene (PP) nanocomposite was prepared with polyaniline/graphene nanocomposite (PANI/GNP) as a green antibacterial additive due to its electrostatic, free radical, and nanoknife effect synergistic antibacterial mechanisms. To improve the dispersibility of PANI/GNP, nanosilica coating on PANI/GNP was constructed successfully with in situ condensation polymerization of epoxy functionalized ethyl orthosilicate to obtain EP‐nSiO2‐PANI/GNP. EP‐nSiO2‐PANI/GNP with a thin nanosilica coating has a significantly improved thermal stability as compared with that of PANI/GNP characterized by TGA. The EP‐nSiO2‐PANI/GNP presents a nanoscale disperse state in PP nanocomposite and thus enhances the melt viscosity and storage modulus accordingly characterized by TEM and Rheology. The EP‐nSiO2‐PANI/GNP/PP filled with 0.5 wt% of EP‐nSiO2‐PANI/GNP demonstrates antibacterial activity of 100% against both Escherichia coli and Staphylococcus aureus.Highlights In situ condensation polymerization to prepare EP‐nSiO2‐PANI/GNP. EP‐nSiO2‐PANI/GNP has enhanced dispersion stability. EP‐nSiO2‐PANI/GNP with a thin nanosilica coating has a good thermal stability. PP nanocomposite with 0.5 wt% filler has excellent antibacterial activity. The electrostatic, free radical, and nanoknife effect antibacterial mechanism.