We present the preparation of advanced antistatic and anticorrosion coatings of polystyrene (PS) incorporating a suitable amount of dodecylbenzenesulfonic acid (DBSA)-doped SiO2@polyaniline (SP) coreshell microspheres. First, aniline-anchored SiO2 (AS) microspheres that were about 850 nm in diameter were synthesized using the conventional base-catalyzed solgel process with tetraethyl orthosilicate in the presence of N-[3-(trimethoxysilyl)propyl]aniline. SP coreshell microspheres were then synthesized by chemical oxidative polymerization of aniline monomers with ammonium persulfate as an oxidizing agent in the presence of the AS microspheres. The polyaniline shell thickness of the as-prepared coreshell microspheres was estimated to be about 120 nm. The AS and SP microspheres were further characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The as-synthesized DBSA-doped SP coreshell microspheres were then blended into PS using N-methyl-2-pyrrolidone as solvent and then cast onto a coldrolled steel (CRS) electrode to obtain antistatic and anticorrosion coatings with a thickness of about 10 mu m. The corrosion protection efficiency of the as-prepared coating materials on the CRS electrode was investigated using a series of systematic electrochemical measurements under saline conditions. The enhanced corrosion protection ability of the PS/SP composite coatings may be attributed to the formation of a dense passive metal oxide layer induced by the redox catalytic effect of the polyaniline shell of the as-synthesized coreshell microspheres, as evidenced by electron spectroscopy for chemical analysis and SEM observations. Moreover, the PS composite coating containing 10 wt% of the SP coreshell microspheres showed an electrical resistance of about 3.65 x 109 cm2, which meets the requirements for antistatic applications. Copyright (c) 2012 Society of Chemical Industry