Fly ash is a complex system with a variety of fine particles. The complex relationship between unburned carbon and ash particles has an important influence on the efficiency of fly ash triboelectrostatic beneficiation. The particles adhered to the two electrode plates are collected through the triboelectrostatic beneficiation experiment. The scanning electron microscopy and X-ray fluorescence are used to detect the microscopic differences between the particles of positive and negative plates. The results show that the flaky carbon particles in the raw ash and the ash particles larger than 4µm are more easily separated, while it is converse for the ash particles with particle size less than 4µm. With the particle size less than 4µm, it is gradually more obvious for the influence of adhesion caused by the roughness surface of spherical unburned carbon particles, and the surface pores structure of porous carbon particles. The binding structure between unburned carbon and ash particles is complex and changeable. It is not beneficial to improve the separation efficiency. Therefore, the micro-structure and micro-morphology have an important effect on fly ash triboelectrostatic beneficiation. Some suggestions were proposed from the microscopic point to improve the efficiency of fly ash triboelectrostatic beneficiation.