Multiwalled carbon nanotube (MWCNT)‐coated polystyrene (PS) beads have been prepared by dispersion polymerization followed by a layer‐by‐layer self‐assembly method. The concentration of carboxylic acid groups on the MWCNTs increased from 1.81 × 1021 to 3.43 × 1022 COO− per g as the treatment time was increased from 3 to 9 h. The sulfonated polystyrene (SPS) beads changed from being negatively charged to positively charged when the cationic polyelectrolyte was self‐assembled on their surface. The surface morphology of the adsorbed polyelectrolyte was smooth without any aggregation and the thickness of the polyelectrolyte coating on the SPS beads was ≈0.6 µm. The electrical conductivity and resistance of the MWCNT‐coated SPS beads were measured to be 4.0 × 10−2 S · cm−1 and 12.8 Ω at a volume fraction of 91%, respectively.
