As the main solid wastes of coal-fired power plants, fly ash particles with different electrical properties are usually recycled using triboelectrostatic separator. The purpose of this study was to investigate the effect of different plate voltages on the separation of fly ash in a rotary triboelectrostatic separator with experiments and numerical simulation. The maximum values of yield of ash products (48.30%), and decarbonisation rate (50.89%) and the minimum loss-on-ignition (6.61%) were obtained when the plate voltage was 24 kV in the separation experiments, while 55.98%, 59.46%, 5.80% were reached respectively when the plate voltage was 26 kV in the simulation. In general, experimental data were similar with numerical simulation. The turning points appeared around 25 kV due to the increasing mismatch in products, which resulted from the reinforced rebound phenomena, namely the charged particle rebound from the electrode plate with a larger reflection velocity, when the plate voltage increased from 18 to 28 kV. It was validated by the numerical simulation results.