We synthesized core–shell type spherical semiconducting poly(2,5-dimethoxyaniline) (PDMA)-coated polystyrene (PS) (PS/PDMA) particles with uniform size and investigated their electrorheological (ER) response. Using monodisperse PS microspheres initially synthesized by dispersion polymerization, 2,5-dimethoxyaniline monomer was pre-adsorbed onto the PS surface via π–π stacking interaction, and then PDMA was synthesized by oxidative polymerization. Morphology of the synthesized PS/PDMA particles was observed by both scanning electron microscopy and transmission electron microscopy, while their chemical compound was confirmed by Fourier transform infrared spectroscopy. The PS/PDMA microspheres were suspended in silicone oil and their ER properties were studied using a rotational rheometer from both steady shear and oscillatory test modes. Flow curves were observed to be fitted well with the Bingham fluid equation, while all three differently measured yield stresses showed similar electric field dependence. Furthermore, dielectric analysis confirmed the degree of relaxation time and polarizability related to the ER behaviors of the PS/PDMA particle-based ER fluid. PS/PDMA particles with several advantages such as easy conductivity control through a doping and a de-doping process, their spherical shape and controllable size are expected to be of great help in their multiple applications in both ER fluids and colloidal science.