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Polyaniline doped with dodecylbenzenesulfonic acid/χ-aluminum oxide (PANDB/χ-Al₂O₃) conducting core-shell nanocomposites was synthesized via an in situ polymerization method in this study. PANDB was synthesized in the presence of dodecylbenzenesulfonic acid (DBSA), which functioned as a dopant and surfactant. The electrical conductivity of the conducting PANDB/χ-Al₂O₃ core-shell nanocomposite was approximately 1.7 × 10⁻¹ S/cm when the aniline/χ-Al₂O₃ (AN/χ-Al₂O₃) weight ratio was 1.5. The transmission electron microscopy (TEM) results indicated that the χ-Al₂O₃ nanoflakes were thoroughly coated by PANDB to form the core-shell (χ-Al₂O₃-PANDB) structure. The TEM and field-emission scanning electron microscopy (FE-SEM) images of the conducting PANDB/χ-Al₂O₃ core-shell nanocomposites also indicated that the thickness of the PANDB layer (shell) could be increased as the weight ratio of AN/χ-Al₂O₃ was increased. In this study, the optimum weight ratio of AN/χ-Al₂O₃ was identified as 1.5. The conducting PANDB/χ-Al₂O₃ core-shell nanocomposite was then blended with water-based polyurethane (WPU) to form a conducting WPU/PANDB/χ-Al₂O₃ blend film. The resulting blend film has promising antistatic and electrostatic discharge (ESD) properties.