The suspensions of ultrafine tourmaline powder in water and n_butanol were prepared by grinding. Ultrafine tourmaline powder was prepared by drying the suspensions through direct heating and azeotropic distillation, according to the properties that water may form azeotrope with n_butanol. TEM shows that drying by direct heating might result in hard aggregation of the tourmaline powder, while hard aggregation might be avoided by azeotropic distillation. Raman spectroscopy reveals that there are O_H and C_H on the surfaces of the tourmaline powder obtained by azeotropic distillation, which indicates that butoxy is chemically adsorbed on the surfaces of tourmaline particles, but not adsorbed on those formed by direct drying. X_ray powder diffraction shows that the intensity of diffraction peaks decreases after grinding. There is no damage to the tourmaline crystal lattice in the process of direct heating, azeotropic distillation, or ultrafine grinding. Therefore, butoxy in n_butanol can be adsorbed chemically on the surfaces of the tourmaline particles in the process of azeotropic distillation, which can effectively prevent the formation of liquid_bridge between the particles of tourmaline and avoid the hard aggregation in the drying process.