AbstractA new technique to control the triboelectric charge (TEC) of polymer microspheres is proposed. Polymer microspheres (PMs) were prepared by three‐component suspension copolymerization of styrene (S), 2‐ethylhexyl methacrylate (EHMA) and dimethylaminoethyl methacrylate (DM). Emulsion particles (EPs) for surface modification were prepared by emulsifier‐free three‐component emulsion copolymerization of S, EHMA and sodium styrene sulfonate (NaSS). PMs were covered with EPs by a process similar to the ‘stepwise heterocoagulation technique’ (Okubo, M., He, Y. & Ichikawa, K., Colloid Polym. Sci., 269 (1991) 125). The value of TEC of modified microspheres varied from ‐ 30 μC/g to ‐ 60 μC/g with increasing NaSS content of EPs from 3wt% to 6wt%, though unmodified particles had small values of TEC. This fact suggests that the surface modification used can lead to the preparation of particles having a desired TEC.