In the course of time, significant amounts of heavy-ion pollutants have been dispersed into the environment. Rapid on-site detection of heavy metal ions is crucial to monitor their dispersion in the nascent stages. In this study, 2.2-μm-diameter polystyrene microspheres (PSM) were synthesized via emulsifier-free polymerization to coat polyacrylonitrile (PSM@PAN) and form core/shell-structured microspheres. Core/shell polystyrene/polyvinyltetrazole (PSM@PVT) microspheres were obtained after a cyano-to-tetrazole conversion reaction, loaded in an electrorheological device (ERD) display constructed using two indium tin oxide glasses with a spacer seal. The ERD loading dispersed the microsphere solution by scattering light through the ERD, resulting in a low transmittance in the absence of an alternating electric field (AEF). Particles in the fluid medium were polarized to induce negative and positive charges at each end of the particles under the AEF, and the resultant particle chains enhanced transmittance. The optimal frequency to generate the highest degree of particle chaining in the presence of an AEF is defined as its characteristic frequency (Fc), which also serves as an indicator to identify the shell materials. The Fc of PSM@PVT shifted from 350 kHz to 30 kHz after adsorbing Cr(VI) from the PVT coating. Transmittance of the ERD loading of PSM@PVT with Cr(VI) increased linearly with the concentration of Cr(VI). Approximately 40 ng mL−1 of the limit of detection was calculated in the linear range of 10–540 ng mL−1. The Fc of the PSM@PVT adsorbing the Cr(VI) was not influenced by Na(I), K(I), Ca(II), Mg(II), Fe(III), and Zn(II) coexisting in the ERD
