As a vital non-metallic mineral resource, cleaning and purification of coal-series kaolin is of importance for the following processing and utilization. This research focused on surface modification to enhance the decarbon-ization performance of coal-series kaolin by triboelectric separation. The effect of citric acid or kerosene on the surface modification and charging performance of kaolinite and coal was explored through Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and charge-to-mass ratio measurements. The results indicated that owing to the adsorption of citric acid or kerosene, the decreased O content and the increased C content of coal enhanced the positive charge on the coal surface, while the decreased Al and Si content of kaolinite improved the negative charge on the kaolinite surface, which enlarged the charge-to-mass ratio gap between coal and kaolinite. Meanwhile, citric acid improved the charging performance of kaolinite and coal more significantly than kerosene. Furthermore, the influence of plate voltage, feeding speed, and friction wheel rotating velocity on the decarbonization performance of coal-series kaolin after surface modifi-cation was studied by triboelectric separation. The separation results indicated that surface modification with citric acid or kerosene improved the triboelectric separation efficiency of coal-series kaolin, and citric acid could realize the more effective separation of coal-series kaolin than kerosene. For 0.125-0.25 mm, 0.074-0.125 mm, and-0.074 mm coal-series kaolin, with citric acid modification, the valuable component recovery was 81.91%, 82.21%, and 82.83%, respectively, and the decarbonization efficiency was 44.66% (increased by 6.56%), 47.19% (increased by 7.00%), and 14.88% (increased by 2.53%), respectively. Our study provides vital guidance for enrichment and purification of coal-series kaolin resource via triboelectric separation.