Ultra-fine zirconium diboride (ZrB2) powders have been synthesized by borothermal reduction reaction, using zirconium oxychloride (ZrOCl2•8H2O) as the precursors of zirconia. The thermodynamic variation in the amorphous ZrO2-B system was studied by thermogravimetric and differential thermal analysis (TG-DTA). The precursors containing amorphous ZrO2 and B were heat-treated under a high heating rate. It is shown that the borothermal reaction can be completed at a relatively low temperature (~950 °C) and short duration (~5 min) under a heating rate of 200 °C/min. The synthesized powders have an average crystalline size of 300 nm with oxygen content less than 2.62 wt%.