Abstract: Mg₂B₂O₅ whiskers with high aspect ratio were synthesized by coprecipitation and sintering process using MgCl₂·6H₂O, H₃BO₃, and NaOH as raw materials and KCl as a flux. Their formation process was investigated by thermogravimetry and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), and scanning electron microcopy (SEM). It is found that the products synthesized at 832℃ are monoclinic Mg₂B₂O₅ whiskers with a diameter of 200-400 nm and a length of 50-80 μm. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) analyses show that the whiskers obtained at 832℃ are single crystalline and grow along with the010 direction. The growth mechanism of Mg₂B₂O₅ whiskers was also presented.